Compounds, processes and marking systems

ABSTRACT

This invention relates to mono- and bis(aryl- and/or heteroaryl)-substituted-phthalazinones, phthalimidines, pyridopyridazinones and pyrrolopyridinones useful as color-forming substances, particularly in electrochromic recording systems, which are prepared by the interaction of a mono- or bis-substituted-phthalide or furopyridinone with a substituted or unsubstituted hydrazine.

BACKGROUND OF THE INVENTION

(a) Field of the Invention

This invention relates to novel compounds classified in the field oforganic chemistry as phthalazinones, phthalimidines,pyridopyridazinones, and pyrrolopyridinones useful as color-formingsubstances, particularly in the art of electrochromic recording; toelectrochromic recording systems containing as the color-formingsubstance said phthalazinones, phthalimidines, pyridopyridazinones andpyrrolopyridinones; and to processes for preparing the phthalazinones,phthalimidines, pyridopyridazinones and pyrrolopyridinones.

(b) Description of the Prior Art

Several classes of organic compounds of widely diverse structural typesare known to be useful as colorless precursors for electrochromicrecording. Among the more important classes, there may be named leucotype dyestuffs such as: phthalides, for example, crystal violet lactone,Malachite green lactone; fluorans, for example,3-diethylamino-5,7-dimethylfluoran; and indolinobenzospiropyrans, forexample, 1,3,3-trimethyl-6'-chloro-8'-methoxyindolinobenzospiropyran.Also utilized as colorless precursors for electrochromic recording,either alone or in admixture with the leuco compounds indicated above,are substances known as redox indicators. The redox indicator whichbecomes colored or discolored in situ in the electrochromic recordingprocess also is generally a leuco body. Among the types of compoundswhich are applicable as redox indicators are phenothiazines, forexample, leuco methylene blue and benzoyl leuco methylene blue. Otherspecific indicators are Leucoethyl Nile Blue, Leucomethyl Capryl Blueand Leucosafranine T. Typical of the many such electrochromic recordingsystems taught in the prior art are those described in U.S. Pat. Nos.3,726,769, 3,871,972, 3,864,684, 4,017,366, 4,133,933, and U.S. Pat. No.Re. 29,427 which issued Apr. 10, 1973, Mar. 18, 1975, Feb. 4, 1975, Apr.12, 1977, Jan. 9, 1979, and Oct. 4, 1977, respectively. The methods forelectrochromic recording taught in the prior art have many variations.However, basically, one or both sides of a sheet of paper is coated ortreated with a coating formulation containing at least one colorlesscolor-forming (leuco) compound. Electrical current is then selectivelyapplied to the coated side of the paper by some means, for example, astylus or a printing head to which an electrical potential can beapplied. The application of the current causes an electrochromicreaction, involving the leuco compound to produce a visible imagecorresponding to the design traced by the stylus or that of the printinghead.

The following items to date appear to constitute the most relevant priorart with regard to the instant invention.

Kuzuya et al. in Chemical Pharmaceutical Bulletin 1980, 28(12), 3561-9(C.A. 94:141182p) describe the preparation and physical characteristicsof 4,4-diaryl-3,4-dihydro-1(2H)-phthalazinones having the structuralformula ##STR1## in which R₁ and R₂ are hydrogen or dimethylamino and R₃is dimethylamino. These phthalazinones are prepared by interacting thecorresponding phthalide with hydrazine hydrate in dilute aqueous ethylalcohol. Although no utility for the compounds is given in thereference, it is taught that the compounds develop a weak green-bluecolor upon exposure to a weak mineral acid such as dilute hydrochloricacid or to bentonite. It is further stated that upon exposure to astrong acid the phthalazinones are converted to phthalimidines. Thephthalazinones are said to show exceptional sensitivity to ultra-violetlight and were found to be excellent initiators for photo-polymerizationof unsaturated compounds.

Japanese Patent Publication No. 8,089,269, published July 5, 1980,discloses and claims phthalazinones having the structural formula##STR2## in which R¹ is hydrogen, lower alkylamino, lower alkyl, loweralkoxy or chlorine; R² is hydrogen or lower alkyl; and R³ is loweralkylamino. The compounds are prepared by heating the correspondingphthalide with hydrazine hydrate. These phthalazinones are disclosed asphotochemical initiators for photo-polymerization of unsaturatedcompounds.

U.S. Pat. No. 4,017,366, issued Apr. 12, 1977, discloses and claims amethod of printing on thermographic paper according to which the heatfor causing the imaging color change in the thermographic coating isgenerated by means of current in a portion of the coating dampened by athin film of a conductive salt solution which is dispersed on thethermographic coating. The current is generated by a printing headhaving spaced electrodes in contact with the dampened portion of thecoating.

Japanese Patent Publication No. 51,050,327, published May 1, 1976discloses phenylhydrazinolactams having the structural formula ##STR3##in which R₁ and R₁₀ represent hydrogen or lower alkyl; R₂ and R₉represent hydrogen or lower alkyl; R₃ and R₈ represent lowermonoalkylamino, lower dialkylamino, N-phenyl-N-lower alkylamino,dibenzylamino, or N-benzyl-N-lower alkylamino; R₄ and R₇ representhydrogen, lower alkyl or halogen; R₅ and R₆ represent hydrogen, halogen,lower alkyl or alkoxy; n represents a number from 1 to 4; m represents anumber from 1 to 5; X represents hydrogen, halogen, lower alkyl, lowermonoalkylamino, lower dialkylamino or acylamino; and Y representshydrogen, halogen or lower alkyl. The compounds are prepared by heatingthe corresponding phthalide with phenylhydrazine. No utility isdisclosed for the phenylhydrazinolactams.

SUMMARY OF THE INVENTION

In its first composition of matter aspect, the invention relates tocertain 3-R¹ -4-X-4-Y-R-1(2H)-phthalazinones useful as colorlessprecursors in electrochromic recording systems.

In its second composition of matter aspect, the invention relates tocertain isomeric mixtures of 7-R¹-8-X-8-Y-pyrido-[2,3d]-pyridazin-5(6H)-ones and 5-X-5-Y-6-R¹-pyrido-[2,3d]-pyridazin-8(5H)-ones useful as colorless precursors inelectrochromic recording systems.

In its third composition of matter aspect, the invention relates tocertain 2-(N-R¹ -amino)-3-X-3-Y-R-phthalimidines useful as colorlessprecursors in electrochromic recording systems.

In a fourth composition of matter aspect, the invention relates tocertain isomeric mixtures of 6-(N-R¹-amino)-7-X-7-Y-(5H)-pyrrolo-[3,4-b]-pyridin-5-ones and 5-X-5-Y-6-(N-R¹-amino)-(7H)-pyrrolo-[3,4-b]-pyridin-7-ones useful as colorlessprecursors in electrochromic recording systems.

The present invention provides in its first article of manufactureaspect, a substrate for use in electrochromic recording systemscomprising a support sheet containing as a color-forming substance a3-R¹ -4-X-4-Y-phthalazin-1(2)-one.

The present invention provides in its second article of manufactureaspect, a substrate for use in electrochromic recording systemscomprising a support sheet containing as a color-forming substance anisomeric mixture of 7-R¹ -8-X-8-Y-pyrido-[2,3-d]-pyridazin-5(6H)-one and5-X-5-Y-6-R¹ -pyrido-[2,3d]-pyridazin-8(5H)-one.

The present invention provides in its third article of manufactureaspect, a substrate for use in electrochromic recording systemscomprising a support sheet containing as a color-forming substance a2-(N-R¹ -amino)-3-X-3-Y-R-phthalimidine.

The present invention provides in its fourth article of manufactureaspect, a substrate for use in electrochromic recording systems asupport sheet containing as a color-forming substance an isomericmixture of 6-(N-R¹ -amino)-7-X-7-Y-(5H)-pyrrolo-[3,4-b]-pyridin-5-oneand 5-X-5-Y-6-(N-R¹ -amino)-(7H)-pyrrolo-[3,4-b]-pyridin-7-one.

In its first process aspect, the invention relates to a process forproducing a compound selected from the group of 3-R¹-4-X-4-Y-R-phthalazin-1(2H)-one and a 2-(N-R¹-amino)-3-X-3-Y-R-phthalimidine and mixtures thereof which comprisesinteracting the corresponding 3-X-3-Y-R-phthalide with the correspondingR¹ substituted hydrazine.

In its second process aspect, the invention relates to a process forproducing a compound selected from the group consisting of an isomericmixture of 7-R¹ -8-X-8-Y-pyrido-[2,3-d]-pyridazin-5(6H)-one and5-X-5-Y-6-R¹ -pyrido-[2,3-d]-pyridazin-8(5H)-one; and an isomericmixture of 6-(N-R¹ -amino)-7-X-7-Y-(5H)-pyrrolo-[3,4-b]-pyridin-5-oneand 5-X-5-Y-6-(N-R¹ -amino)-[7H]-pyrrolo-[3,4-b]-pyridin-7-one whichcomprises interacting the corresponding isomeric mixture of7-X-7-Y-furo-[2,3-b]-pyridin-7(5H)-one with the corresponding R¹substituted hydrazine.

DETAILED DESCRIPTION INCLUSIVE OF THE PREFERRED EMBODIMENTS

More specifically, this invention in its first composition of matteraspect, resides in the novel 3-R¹-4-X-4-Y-R-dihydrophthalazin-1(2H)-ones which are particularly useful ascolorless precursors in the art of electrochromic recording having thestructural formula ##STR4## wherein: R represents hydrogen, dialkylaminoin which alkyl is non-tertiary C₁ to C₄ alkyl, COOR² in which R² ishydrogen or non-tertiary C₁ to C₁₆ alkyl or one to four halo; R¹ ishydrogen, C₁ to C₃ alkyl, pyridyl, CZ in which Z is non-tertiary C₁ toC₄ alkoxy, NHNH₂ or non-tertiary C₁ to C₄ alkyl, phenyl or phenylsubstituted by one or two of C₁ to C₃ alkyl, non-tertiary C₁ to C₄alkoxy, halo, nitro or amino; X is selected from the group consisting of##STR5## and Y is selected from the group consisting of hydrogen,##STR6## in which R³ and R⁹ independently represent hydrogen,non-tertiary C₁ to C₄ alkyl, non-tertiary C₁ to C₄ alkoxy, acylamino inwhich acyl is non-tertiary C₂ to C₄ alkyl or dialkylamino in which alkylis non-tertiary C₁ to C₄ alkyl, R⁴ and R¹⁰ independently representnon-tertiary C₁ to C₄ alkyl, benzyl or benzyl substituted in the benzenering by one or two of halo or C₁ to C₃ alkyl, R⁵ and R¹¹ independentlyrepresent non-tertiary C₁ to C₄ alkyl, benzyl or benzyl substituted inthe benzene ring by one or two of halo or C₁ to C₃ alkyl, R⁶ and R¹²independently represent hydrogen, non-tertiary C₁ to C₁₆ alkyl,non-tertiary C₂ to C₈ alkylene, phenoxyethyl, benzyl or benzylsubstituted in the benzene ring by one or two of halo or non-tertiary C₁to C₄ alkyl, R⁷ and R¹³ independently represent hydrogen, C₁ to C₃ alkylor phenyl, and R⁸ and R¹⁴ independently represent hydrogen, halo,non-tertiary C₁ to C₄ alkyl, non-tertiary C₁ to C₄ alkoxy or nitro withthe proviso that when R³ and R⁹ are both hydrogen, R⁴, R⁵, R¹⁰ and R¹¹can not simultaneously be non-tertiary C₁ to C₄ alkyl.

Preferred compounds within the ambit of the first composition of matteraspect are the novel 3-R¹ -4-Y-4-(2-R³ -4-N-R⁴ -N-R⁵-aminophenyl)-R-phthalazin-1(2H)-ones of Formula I wherein X is 2-R³-4-N-R⁴ -N-R⁵ -aminophenyl having the structural formula ##STR7## inwhich R, R¹, R³, R⁴, R⁵ and Y each have the same respective meaningsgiven in Formula I; the novel 3-R¹ -4-[2-R³ -4-(N-R⁴ -N-R⁵-amino)phenyl]-4-[2-R⁹ -4-(N-R¹⁰ -N-R¹¹-amino)phenyl]-R-phthalazin-1(2H)-ones of Formula I wherein X is 2-R³-4-(N-R⁴ -N-R⁵ -amino)phenyl and Y is 2-R⁹ -4-(N-R¹⁰ -N-R¹¹-amino)phenyl having the structural formula ##STR8## in which R, R¹, R³,R⁴, R⁵, R⁹, R¹⁰ and R¹¹ each have the same respective meanings given inFormula II; the novel 3-R¹ -4-[2-R³ -4-(N-R⁴ -N-R⁵-amino)phenyl]-4-(1-R¹² -2-R¹³ -5/6-R¹⁴-indol-3-yl)-R-phthalazin-1(2H)-ones of Formula I wherein X is 2-R³-4-(N-R⁴ -N-R⁵ -amino)phenyl and Y is 1-R¹² -2-R¹³ -5/6-R¹⁴ -indol-3-ylhaving the structural formula ##STR9## in which R, R¹, R³, R⁴, R⁵, R¹²,R¹³ and R¹⁴ each have the same respective meanings given in Formula I;and the novel 3-R¹ -4-(1-R⁶ -2-R⁷ -5/6-R⁸ -indol-3-yl)-4-(1-R¹² -2-R¹³-5/6-R¹⁴ -indol-3-yl)-R-phthalazin-1(2H)-ones of Formula I wherein X is1-R⁶ -2-R⁷ -5/6-R⁸ -indol-3-yl and Y is 1-R¹² -2-R¹³ -5/6-R¹⁴-indol-3-yl having the structural formula ##STR10## in which R, R¹, R⁶,R⁷, R⁸, R¹², R¹³ and R¹⁴ each have the same respective meanings given inFormula I.

In a second composition of matter aspect, the invention sought to bepatented resides in the novel isomeric mixture of 7-R¹-8-X-8-Y-pyrido-[2,3-d]-pyridazin-5(6H)-ones and 5-X-5-Y-6-R¹-pyrido-[2,3-d]-pyridazin-8(5H)-ones having the structural formulas,respectively ##STR11## wherein: R¹ is hydrogen, C₁ to C₃ alkyl, pyridyl,##STR12## in which Z is non-tertiary C₁ to C₄ alkoxy, NHNH₂ ornon-tertiary C₁ to C₄ alkyl, phenyl or phenyl substituted by one or twoof C₁ to C₃ alkyl, non-tertiary C₁ to C₄ alkoxy, halo, nitro or amino; Xis selected from the group consisting of ##STR13## and Y is selectedfrom the group consisting of hydrogen, ##STR14## in which R³ and R⁹independently represent hydrogen, non-tertiary C₁ to C₄ alkyl,non-tertiary C₁ to C₄ alkoxy, acylamino in which acyl is non-tertiary C₂to C₄ alkyl or dialkylamino in which alkyl is non-tertiary C₁ to C₄alkyl, R⁴ and R¹⁰ independently represent non-tertiary C₁ to C₄ alkyl,benzyl or benzyl substituted in the benzene ring by one or two of haloor C₁ to C₃ alkyl, R⁵ and R¹¹ indenpendently represent non-tertiary C₁to C₄ alkyl, benzyl or benzyl substituted in the benzene ring by one ortwo of halo or C₁ to C₃ alkyl, R⁶ and R¹² independently representhydrogen, non-tertiary C₁ to C₁₆ alkyl, non-tertiary C₂ to C₈ alkylene,phenoxyethyl, benzyl or benzyl substituted in the benzene ring by one ortwo of halo or non-tertiary C₁ to C₄ alkyl, R⁷ and R.sup. 13independently represent hydrogen, C₁ to C₃ alkyl or phenyl, and R⁸ andR¹⁴ independently represent hydrogen, halo, non-tertiary C₁ to C₄ alkyl,non-tertiary C₁ to C₄ alkoxy or nitro.

Preferred compounds within the ambit of the second composition of matteraspect are the novel isomeric mixtures of 7-R¹ -8-[2-R³ -4-(N-R⁴ -N-R⁵-amino)phenyl]-8-(1-R¹² -2-R¹³ -5/6-R¹⁴-indol-3-yl)-pyrido-[2,3-d]-pyridazin-5(6H)-one and 5-(2-R³ -4-N-R⁴-N-R⁵ -aminophenyl)-5-(1-R¹² -2-R¹³ -5/6-R¹⁴ -indol-3-yl)-6-R¹-pyrido-[2,3-d]-pyridazin-8(5H)-ones having the structural formulas,respectively ##STR15## in which R¹, R³, R⁴, R⁵, R¹², R¹³ and R¹⁴ eachhave the same respective meanings given in Formulas VI and VII; and thenovel isomeric mixture of 7-R¹ -8-(1-R⁶ -2-R⁷ -5/6-R⁸-indol-3-yl)-8-(1-R¹² -2-R¹³ -5/6-R¹⁴-indol-3-yl)-pyrido-[2,3-d]-pyridazin-5(6H)-one and 5-(1-R⁶ -2-R⁷-5/6-R⁸ -indol-3-yl)-5-(1-R¹² -2-R¹³ -5/6-R¹⁴ -indol-3-yl)-6-R¹-pyrido-[2,3-d]-pyridazin-8(5H)-one having the structural formulas,respectively ##STR16## in which R¹, R⁶, R⁷, R⁸, R¹², R¹³ and R¹⁴ eachhave the same respective meanings given in Formulas VI and VII.

In a third composition of matter aspect, the invention sought to bepatented resides in the novel 2-(N-R¹ -amino)-3-X-3-Y-R-phthalimidineshaving the formula ##STR17## wherein: R represents hydrogen,dialkylamino in which alkyl is non-tertiary C₁ to C₄ alkyl, COOR² inwhich R² is hydrogen or non-tertiary C₁ to C₁₆ alkyl or one to fourhalo; R¹ represents hydrogen, C₁ to C₃ alkyl, pyridyl, ##STR18## inwhich Z is non-tertiary C₁ to C₄ alkoxy, NHNH₂ or non-tertiary C₁ to C₄alkyl, phenyl or phenyl substituted by one or two of C₁ to C₃ alkyl,non-tertiary C₁ to C₄ alkoxy, halo, nitro or amino; X is selected fromthe group consisting of ##STR19## and Y is selected from the groupconsisting of hydrogen, ##STR20## in which R³ and R⁹ independentlyrepresent hydrogen, non-tertiary C₁ to C₄ alkyl, non-tertiary C₁ to C₄alkoxy, acylamino in which acyl is non-tertiary C₂ to C₄ alkyl ordialkylamino in which alkyl is non-tertiary C₁ to C₄ alkyl, R⁴ and R¹⁰independently represent non-tertiary C₁ to C₄ alkyl, benzyl or benzylsubstituted in the benzene ring by one or two of halo or C₁ to C₃ alkyl,R⁵ and R¹¹ independently represent non-tertiary C₁ to C₄ alkyl, benzylor benzyl substituted in the benzene ring by one or two of halo or C₁ toC₃ alkyl, R⁶ and R¹² independently represent hydrogen, non-tertiary C₁to C₁₆ alkyl, non-tertiary C₂ to C₈ alkylene, phenoxyethyl, benzyl orbenzyl substituted in the benzene ring by one or two of halo ornon-tertiary C₁ to C₄ alkyl, R⁷ and R¹³ independently representhydrogen, C₁ to C₃ alkyl or phenyl, and R⁸ and R¹⁴ independentlyrepresent hydrogen, halo, non-tertiary C₁ to C₄ alkyl, non-tertiary C₁to C₄ alkoxy or nitro with the proviso that when R³ and R⁹ are bothhydrogen, R⁴, R⁵, R¹⁰ and R¹¹ can not simultaneously be non-tertiary C₁to C₄ alkyl.

Preferred compounds within the ambit of the third composition of matteraspect are the novel 2-(N-R¹ -amino)-3-[2-R³ -4-(N-R⁴ -N-R⁵-amino)phenyl]-3-Y-5/6-R-phthalimidines having the structural formula##STR21## in which R, R¹, R³, R⁴, R⁵ and Y each have the same respectivemeanings given in Formula XII; the novel 2-(N-R¹ -amino)-3-[2-R³-4-N-(R⁴ -N-R⁵ -amino)phenyl]-3-(2-R⁹ -4-N-R¹⁰ -N-R¹¹-aminophenyl)-5/6-R-phthalimidines having the structural formula##STR22## in which R, R¹, R³, R⁴, R⁵, R⁹, R¹⁰ and R¹¹ each have the samerespective meanings given in Formula XII; the novel 2-(N-R¹-amino)-3-[2-R³ -4-(N-R⁴ -N-R⁵ -amino)phenyl]-3-(1-R¹² -2-R¹³ -5/6-R¹⁴-indol-3-yl)-5/6-R-phthalimidines having the structural formula##STR23## in which R, R¹, R³, R⁴, R⁵, R¹², R¹³ and R¹⁴ each have thesame respective meanings given in Formula XII; and the novel 2-(N-R¹-amino)-3-(1-R⁶ -2-R⁷ -5/6-R⁸ -indol-3-yl)-3-(1-R¹² -2-R¹³ -5/6-R¹⁴-indol-3-yl)-5/6-R-phthalimidine having the structural formula ##STR24##in which R, R¹, R⁶, R⁷, R⁸, R¹², R¹³ and R¹⁴ each have the samerespective meanings given in Formula XII.

In a fourth composition of matter aspect, the invention sought to bepatented resides in the novel isomeric mixtures of compounds having thestructural formulas ##STR25## wherein: R¹ is hydrogen, C₁ to C₃ alkyl,pyridyl, ##STR26## in which Z is non-tertiary C₁ to C₄ alkoxy, NHNH₂ ornon-tertiary C₁ to C₄ alkyl, phenyl or phenyl substituted by one or twoof C₁ to C₃ alkyl, non-tertiary C₁ to C₄ alkoxy, halo, nitro or amino; Xis selected from the group consisting of ##STR27## and Y is selectedfrom the group consisting of hydrogen, ##STR28## in which R³ and R⁹independently represent hydrogen, non-tertiary C₁ to C₄ alkyl,non-tertiary C₁ to C₄ alkoxy, acylamino in which acyl is non-tertiary C₂to C₄ alkyl or dialkylamino in which alkyl is non-tertiary C₁ to C₄alkyl, R⁴ and R¹⁰ independently represent non-tertiary C₁ to C₄ alkyl,benzyl or benzyl substituted in the benzene ring by one or two of haloor C₁ to C₃ alkyl, R⁵ and R¹¹ independently represent non-tertiary C₁ toC₄ alkyl, benzyl or benzyl substituted in the benzene ring by one or twoof halo or C₁ to C₃ alkyl, R⁶ and R¹² independently represent hydrogen,non-tertiary C₁ to C₁₆ alkyl, non-tertiary C₂ to C₈ alkylene,phenoxyethyl, benzyl or benzyl substituted in the benzene ring by one ortwo of halo or non-tertiary C₁ to C₄ alkyl, R⁷ and R¹³ independentlyrepresent hydrogen, C₁ to C₃ alkyl or phenyl, and R⁸ and R¹⁴independently represent hydrogen, halo, non-tertiary C₁ to C₄ alkyl,non-tertiary C₁ to C₄ alkoxy or nitro.

Preferred compounds within the ambit of the fourth composition of thematter aspect are the novel isomeric mixtures of 6-(N-R¹ -amino)-7-[2-R³-4-(N-R⁴ -N-R⁵ -amino)phenyl]-7-(1-R¹² -2-R¹³ -5/6-R¹⁴-indol-3-yl)-(5H)-pyrrolo-[3,4-b]-pyridin-5-ones and 5-[2-R³ -4-(N-R⁴-N-R⁵ -amino)phenyl]-5-(1-R¹² -2-R¹³ -5/6-R¹⁴ -indol-3-yl)-6-(N-R¹-amino)-(7H)-pyrrolo-[3,4-b]-pyridin-7-ones having the structuralformulas ##STR29## in which R¹, R³, R⁴, R⁵, R¹², R¹³ and R¹⁴ each havethe same respective meanings given in Formulas XVII and XVIII; and thenovel isomeric mixtures of 6-(N-R¹ -amino)-7-(1-R⁶ -2-R⁷ -5/6-R⁸-indol-3-yl)-7-(1-R¹² -2-R¹³ -5/6-R¹⁴-indol-3-yl)-(5H)-pyrrolo-[3,4-b)-pyridin-5-ones and 5-(1-R⁶ -2-R⁷-5/6-R⁸ -indol-3-yl)-5-(1-R¹² -2-R¹³ -5/6-R¹⁴ -indol-3-yl)-6-(N-R¹-amino)-(7H)-pyrrolo-[3,4-b]-pyridin-7-ones having the structuralformulas ##STR30## in which R, R¹, R⁶, R⁷, R⁸, R¹², R¹³ and R¹⁴ eachhave the same respective meanings given in Formulas XVII and XVIII.

In the first of its article of manufacture aspects, the invention soughtto be patented resides in a substrate for use in electrochromicrecording comprising a support sheet containing as a color-formingsubstance a 3-R¹ -4-X-4-Y-R-phthalazin-1(2H)-one having the structuralformula ##STR31## wherein: R represents hydrogen, dialkylamino in whichalkyl is non-tertiary C₁ to C₄ alkyl, COOR² in which R² is hydrogen ornon-tertiary C₁ to C₁₆ alkyl or one to four halo; R¹ is hydrogen, C₁ toC₃ alkyl, pyridyl, ##STR32## in which Z is non-tertiary C₁ to C₄ alkoxy,NHNH₂ or non-tertiary C₁ to C₄ alkyl, phenyl or phenyl substituted byone or two of C₁ to C₃ alkyl, non-tertiary C₁ to C₄ alkoxy, halo, nitroor amino; X is selected from the group consisting of ##STR33## and Y isselected from the group consisting of hydrogen, ##STR34## in which R³and R⁹ independently represent hydrogen, non-tertiary C₁ to C₄ alkyl,non-tertiary C₁ to C₄ alkoxy, acylamino in which acyl is non-tertiary C₂to C₄ alkyl or dialkylamino in which alkyl is non-tertiary C₁ to C₄alkyl, R⁴ and R¹⁰ independently represent non-tertiary C₁ to C₄ alkyl,benzyl or benzyl substituted in the benzene ring by one or two of haloor C₁ to C₃ alkyl, R⁵ and R¹¹ independently represent non-tertiary C₁ toC₄ alkyl, benzyl or benzyl substituted in the benzene ring by one or twoof halo or C₁ to C₃ alkyl, R⁶ and R¹² independently represent hydrogen,non-tertiary C₁ to C₁₆ alkyl, non-tertiary C₂ to C₈ alkylene,phenoxyethyl, benzyl or benzyl substituted in the benzene ring by one ortwo of halo or non-tertiary C₁ to C₄ alkyl, R⁷ and R¹³ independentlyrepresent hydrogen, C₁ to C₃ alkyl or phenyl, and R₈ and R¹⁴independently represent hydrogen, halo, non-tertiary C₁ to C₄ alkyl,non-tertiary C₁ to C₄ alkoxy or nitro.

Preferred articles within the ambit of first article of manufacture arethose wherein the color-forming component comprises a 3-R¹ -4-Y-4-[2-R³-4-(N-R⁴ -N-R⁵ -amino)-phenyl]-6/7-R-phthalazin-1(2H)-one of Formula IIwherein R, R¹, R³, R⁴, R⁵ and Y each have the same respective meaningsgiven in Formula I; a 3-R¹ -[2-R³ -4-(N-R⁴ -N-R⁵ -amino)phenyl]-4-[2-R⁹-4-(N-R¹⁰ -N-R¹¹ -amino)phenyl]-6/7-R-phthalazin-1(2H)-one of FormulaIII wherein R, R¹, R³, R⁴, R⁵, R⁹, R¹⁰ and R¹¹ each have the samerespective meanings given in Formula I; a 3-R¹ -4-[2-R³ -4-(N-R⁴ -N-R⁵-amino)phenyl)-4-(1-R¹² -2-R¹³ -5/6-R¹⁴-indol-3-yl)-6/7-R-phthalazin-1(2H)-one of Formula IV wherein R, R¹, R³,R⁴, R⁵, R¹², R¹³ and R¹⁴ each have the same respective meanings given inFormula I; and a 3-R¹ -4-(1-R⁶ -2-R⁷ -5/6-R⁸ -indol-3-yl)-4-(1-R¹²-2-R¹³ -5/6-R¹⁴ -indol-3-yl)-6/7-R-phthalazin-1(2H)-one of Formula Vwherein R, R¹, R⁶, R⁷, R⁸, R¹², R¹³ and R¹⁴ each have the samerespective meanings given in Formula I.

In a second article of manufacture aspect, the invention sought to bepatented resides in the novel substrate for use in electrochromicrecording containing as a color-forming substance an isomeric mixture of7-R¹ -8-X-8-Y-pyrido-[2,3-d]-pyridazin-5(6H)-ones of Formula VI and5-X-5-Y-6-R¹ -pyrido-[2,3-d]-pyridazin-8(5H)-ones of Formula VII havingthe structural formulas, respectively ##STR35## wherein: R¹ is hydrogen,C₁ to C₃ alkyl, pyridyl, ##STR36## in which Z is non-tertiary C₁ to C₄alkoxy, NHNH₂ or non-tertiary C₁ to C₄ alkyl, phenyl or phenylsubstituted by one or two of C₁ to C₃ alkyl, non-tertiary C₁ to C₄alkoxy, halo, nitro or amino; X is selected from the group consisting of##STR37## and Y is selected from the group consisting of hydrogen,##STR38## in which R³ and R⁹ independently represent hydrogen,non-tertiary C₁ to C₄ alkyl, non-tertiary C₁ to C₄ alkoxy, acylamino inwhich acyl is non-tertiary C₂ to C₄ alkyl or dialkylamino in which alkylis non-tertiary C₁ to C₄ alkyl, R⁴ and R¹⁰ independently representnon-tertiary C₁ to C₄ alkyl, benzyl or benzyl substituted in the benzenering by one or two of halo or C₁ to C₃ alkyl, R⁵ and R¹¹ independentlyrepresent non-tertiary C₁ to C₄ alkyl, benzyl or benzyl substituted inthe benzene ring by one or two or halo or C₁ to C₃ alkyl, R⁶ and R¹²independently represent hydrogen, non-tertiary C₁ to C₁₆ alkyl,non-tertiary C₂ to C₈ alkylene, phenoxyethyl, benzyl or benzylsubstituted in the benzene ring by one or two of halo or non-tertiary C₁to C₄ alkyl, R⁷ and R¹³ independently represent hydrogen, C₁ to C₃ alkylor phenyl, and R⁸ and R¹⁴ independently represent hydrogen, halo,non-tertiary C₁ to C₄ alkyl, non-tertiary C₁ to C₄ alkoxy or nitro.

Preferred articles within the ambit of the second article of manufactureare those wherein the color-forming component comprises an isomericmixture of 7-R¹ -8-[2-R³ -4-(N-R⁴ -N-R⁵ -amino)phenyl]-8-(1-R¹² -2-R¹³-5/6-R¹⁴ -indol-3-yl)-pyrido-[2,3-d]-pyridazin-5(6H)-ones of FormulaVIII and 5-[2-R³ -4-(N-R⁴ -N-R⁵ -amino)phenyl]-5-(1-R¹² -2-R¹³ -5/6-R¹⁴-indol-3-yl)-pyrido-[2,3-d]-pyridazin-8(5H)-ones of Formula IX in whichR¹, R³, R⁴, R⁵, R¹², R¹³ and R¹⁴ each have the same respective meaningsgiven in Formulas VI and VII; and an isomeric mixture of 7-R¹ -8-(1-R⁶-2-R⁷ -5/6-R⁸ -indol-3-yl)-8-(1-R¹² -2-R¹³ -5/6-R¹⁴-indol-3-yl)-pyrido-[2,3-d]-pyridazin-5(6H)-ones of Formula X and5-(1-R⁶ -2-R⁷ -5/6-R⁸ -indol-3-yl)-5-(1-R¹² -2-R¹³ -5/6-R¹⁴-indol-3-yl)-6-R¹ -pyrido-[2,3-d]-pyridazin-8(5H)-ones of Formula XII inwhich R¹, R⁶, R⁷, R⁸, R¹², R¹³ and R¹⁴ each have the same respectivemeanings given in Formulas VI and VII.

In a third article of manufacture aspect, the invention sought to bepatented resides in the novel substrate for use in electrochromicrecording containing as a color-forming substance the novel 2-(N-R¹-amino)-3-X-3-Y-R-phthalimidines of Formula XII having the formula##STR39## wherein: R represents hydrogen, dialkylamino in which alkyl isnon-tertiary C₁ to C₄ alkyl, COOR² in which R² is hydrogen ornon-tertiary C₁ to C₁₆ alkyl or one to four halo; R¹ representshydrogen, C₁ to C₃ alkyl, pyridyl, ##STR40## in which Z is non-tertiaryC₁ to C₄ alkoxy, NHNH₂ or non-tertiary C₁ to C₄ alkyl, phenyl or phenylsubstituted by one or two of C₁ to C₃ alkyl, non-tertiary C₁ to C₄alkoxy, halo, nitro or amino; X is selected from the group consisting of##STR41## and Y is selected from the group consisting of hydrogen,##STR42## in which R³ and R⁹ independently represent hydrogen,non-tertiary C₁ to C₄ alkyl, non-tertiary C₁ to C₄ alkoxy, acylamino inwhich acyl is non-tertiary C₂ to C₄ alkyl or dialkylamino in which alkylis non-tertiary C₁ to C₄ alkyl, R⁴ and R¹⁰ independently representnon-tertiary C₁ to C₄ alkyl, benzyl or benzyl substituted in the benzenering by one or two of halo or C₁ to C₃ alkyl, R⁵ and R¹¹ independentlyrepresent non-tertiary C₁ to C₄ alkyl, benzyl or benzyl substituted inthe benzene ring by one or two or halo or C₁ to C₃ alkyl, R⁶ and R¹² lindependently represent hydrogen, non-tertiary C₁ to C₁₆ alkyl,non-tertiary C₂ to C₈ alkylene, phenoxyethyl, benzyl or benzylsubstituted in the benzene ring by one or two of halo or non-tertiary C₁to C₄ alkyl, R⁷ and R¹³ independently represent hydrogen, C₁ to C₃ alkylor phenyl, and R⁸ and R¹⁴ independently represent hydrogen, halo,non-tertiary C₁ to C₄ alkyl, non-tertiary C₁ to C₄ alkoxy or nitro withthe proviso that when R³ and R⁹ are both hydrogen, R⁴, R⁵, R¹⁰ and R¹¹can not simultaneously be non-tertiary C₁ to C₄ alkyl.

Preferred articles within the third article of manufacture aspect arethose wherein the color-forming component comprises a 2-(N-R¹-amino)-3-[2-R³ -4-(N-R⁴ -N-R⁵ -amino)phenyl]-3-Y-R-phthalimidine ofFormula XIII in which R, R¹, R³, R⁴, R⁵ and Y each have the samerespective meanings given in Formula XII; a 2-(N-R¹ -amino)-3-[2-R³-4-(N-R⁴ -N-R⁵ -amino)phenyl]-3-[2-R⁹ -4-(N-R¹⁰ -N-R¹¹-amino)phenyl]-R-phthalimidine of Formula XIV in which R, R¹, R³, R⁴,R⁵, R⁹, R¹⁰ and R¹¹ each have the same respective meanings given inFormula XII; a 2-(N-R¹ -amino)-3-[2-R³ -4-(N-R⁴ -(N-R⁵-amino)-phenyl]-3-(1-R¹² -2-R¹³ -5/6-R¹⁴ -indol-3-yl)-R-phthalimidine ofFormula XV in which R, R¹, R⁴, R⁵, R⁶, R¹², R¹³ and R¹⁴ each have thesame respective meanings given in Formula XIV; and a 2-(N-R¹-amino)-3-(1-R⁶ -2-R⁷ -5/6-R⁸ -indol-3-yl)-3-(1-R¹² -2-R¹³ -5/6-R¹⁴-indol-3-yl)-R-phthalimidine of Formula XVI in which R, R¹, R⁶, R⁷, R⁸,R¹², R¹³ and R¹⁴ each have the same respective meanings given in FormulaXII.

In a fourth article of manufacture aspect, the invention sought to bepatented resides in the novel substrate for use in electrochromicrecording containing as a color-forming substance the novel isomericmixtures of 6-(N-R¹ -amino)-7-X-7-Y-(5H)-pyrrolo-[3,4-b]-pyridin-5-onesof Formula XVII and 5-X-5-Y-6-(N-R¹-amino)-(7H)-pyrrolo-[3,4-b]-pyridin-7-ones of Formula XVIII having thestructural formulas ##STR43## wherein: R¹ is hydrogen, C₁ to C₃ alkyl,pyridyl, ##STR44## in which Z is non-tertiary C₁ to C₄ alkoxy, NHNH₂ ornon-tertiary C₁ to C₄ alkyl, phenyl or phenyl substituted by one or twoof C₁ to C₃ alkyl, non-tertiary C₁ to C₄ alkoxy, halo, nitro or amino; Xis selected from the group consisting of ##STR45## and Y is selectedfrom the group consisting of hydrogen, ##STR46## in which R³ and R⁹independently represent hydrogen, non-tertiary C₁ to C₄ alkyl,non-tertiary C₁ to C₄ alkoxy, acylamino in which acyl is non-tertiary C₂to C₄ alkyl or dialkylamino in which alkyl is non-tertiary C₁ to C₄alkyl, R⁴ and R¹⁰ independently represent non-tertiary C₁ to C₄ alkyl,benzyl or benzyl substituted in the benzene ring by one or two of haloor C₁ to C₃ alkyl, R⁵ and R¹¹ independently represent non-tertiary C₁ toC₄ alkyl, benzyl or benzyl substituted in the benzene ring by one or twoor halo or C₁ to C₃ alkyl, R⁶ and R¹² independently represent hydrogen,non-tertiary C₁ to C₁₆ alkyl, non-tertiary C₂ to C₈ alkylene,phenoxyethyl, benzyl or benzyl substituted in the benzene ring by one ortwo of halo or non-tertiary C₁ to C₄ alkyl, R⁷ and R.sup. 13independently represent hydrogen, C₁ to C₃ alkyl or phenyl, and R⁸ andR¹⁴ independently represent hydrogen, halo, non-tertiary C₁ to C₄ alkyl,non-tertiary C₁ to C₄ alkoxy or nitro.

Preferred articles within the fourth article of manufacture are thosewherein the color-forming component comprises an isomeric mixture of6-(N-R¹ -amino)-7-[2-R³ -4-(N-R⁴ -N-R⁵ -amino)phenyl]-7-(1-R¹² -2-R¹³-5/6-R¹⁴ -indol-3-yl)-(5H)-pyrrolo-[3,4-b]-pyridin-5-ones of Formula XIXand 5-[2-R³ -4-(N-R⁴ -N-R⁵ -amino)phenyl]-5-(1-R¹² -2-R¹³ -5/6-R¹⁴-indol-3-yl)-6-(N-R¹ -amino)-(7H)-pyrrolo-[3,4-b]-pyridin-7-ones ofFormula XX in which R¹, R³, R⁴, R⁵, R¹², R¹³ and R¹⁴ each have the samerespective meanings given in Formulas XVII and XVIII; and an isomericmixture of 6-(N-R¹ -amino)-7-(1-R⁶ -2-R⁷ -5/6-R⁸ -indol-3-yl)-7-(1-R¹²-2-R¹³ -5/6-R¹⁴ -indol-3-yl)-(5H)-pyrrolo-[3,4-b]-pyridin-7-ones ofFormula XX and 5-(1-R⁶ -2-R⁷ -5/6-R⁸ -indol-3-yl)-5-(1-R¹² -2-R¹³-5/6-R¹⁴ -indol-3-yl)-6-(N-R¹-amino)-(7H)-pyrrolo-[3,4-b]-pyridin-7-ones of Formula XXII in which R¹,R⁶, R⁷, R⁸, R¹², R¹³ and R¹⁴ each have the same respective meaningsgiven in Formulas XVII and XVIII.

In its first process aspect, the invention sought to be patented residesin the process for preparing a compound selected from the group havingthe structural formulas ##STR47## and mixtures thereof wherein: Rrepresents hydrogen, dialkylamino in which alkyl is non-tertiary C₁ toC₄ alkyl, COOR² in which R² is hydrogen or non-tertiary C₁ to C₁₆ alkylor one to four halo; R¹ represents hydrogen, C₁ to C₃ alkyl, pyridyl,##STR48## in which Z is non-tertiary C₁ to C₄ alkoxy, NHNH₂ ornon-tertiary C₁ to C₄ alkyl, phenyl or phenyl substituted by one or twoof C₁ to C₃ alkyl, non-tertiary C₁ to C₄ alkoxy, halo, nitro or amino; Xis selected from the group consisting of ##STR49## and Y is selectedfrom the group consisting of hydrogen, ##STR50## in which R³ and R⁹independently represent hydrogen, non-tertiary C₁ to C₄ alkyl,non-tertiary C₁ to C₄ alkoxy, acylamino in which acyl is non-tertiary C₂to C₄ alkyl or dialkylamino in which alkyl is non-tertiary C₁ to C₄alkyl, R⁴ and R¹⁰ independently represent non-tertiary C₁ to C₄ alkyl,benzyl or benzyl substituted in the benzene ring by one or two of haloor C₁ to C₃ alkyl, R⁵ and R¹¹ independently represent non-tertiary C₁ toC₄ alkyl, benzyl or benzyl substituted in the benzene ring by one or twoor halo or C₁ to C₃ alkyl, R⁶ and R¹² independently represent hydrogen,non-tertiary C₁ to C₁₆ alkyl, non-tertiary C₂ to C₈ alkylene,phenoxyethyl, benzyl or benzyl substituted in the benzene ring by one ortwo of halo or non-tertiary C₁ to C₄ alkyl, R⁷ and R¹³ independentlyrepresent hydrogen, C₁ to C₃ alkyl or phenyl, and R⁸ and R¹⁴independently represent hydrogen, halo, non-tertiary C₁ to C₄ alkyl,non-tertiary C₁ to C₄ alkoxy or nitro with the proviso that when R³ andR⁹ are both hydrogen, R⁴, R⁵, R¹⁰ and R¹¹ can not simultaneously benon-tertiary C₁ to C₄ alkyl which comprises interacting a compoundhaving the structural formula ##STR51## with a compound of thestructural formula

    R.sup.1 NHNH.sub.2

Formula XXIV

In its second process aspect, the invention sought to be patentedresides in the process for preparing a compound selected from the grouphaving the structural formulas ##STR52## and mixtures thereof wherein:R¹ is hydrogen, C₁ to C₃ alkyl, pyridyl, ##STR53## in which Z isnon-tertiary C₁ to C₄ alkoxy, NHNH₂ or non-tertiary C₁ to C₄ alkyl,phenyl or phenyl substituted by one or two of C₁ to C₃ alkyl,non-tertiary C₁ to C₄ alkoxy, halo, nitro or amino; X is selected fromthe group consisting of ##STR54## and Y is selected from the groupconsisting of hydrogen, ##STR55## in which R³ and R⁹ independentlyrepresent hydrogen, non-tertiary C₁ to C₄ alkyl, non-tertiary C₁ to C₄alkoxy, acylamino in which acyl is non-tertiary C₂ to C₄ alkyl ordialkylamino in which alkyl is non-tertiary C₁ to C₄ alkyl, R⁴ and R¹⁰independently represent non-tertiary C₁ to C₄ alkyl, benzyl or benzylsubstituted in the benzene ring by one or two of halo or C₁ to C₃ alkyl,R⁵ and R¹¹ independently represent non-tertiary C₁ to C₄ alkyl, benzylor benzyl substituted in the benzene ring by one or two or halo or C₁ toC₃ alkyl, R⁶ and R¹² independently represent hydrogen, non-tertiary C₁to C₁₆ alkyl, non-tertiary C₂ to C₈ alkylene, phenoxyethyl, benzyl orbenzyl substituted in the benzene ring by one or two of halo ornon-tertiary C₁ to C₄ alkyl, R⁷ and R¹³ independently representhydrogen, C₁ to C₃ alkyl or phenyl, and R⁸ and R¹⁴ independentlyrepresent hydrogen, halo, non-tertiary C₁ to C₄ alkyl, non-tertiary C₁to C₄ alkoxy or nitro which comprises interacting an isomeric mixturehaving the structural formulas ##STR56## with a compound having thestructural formula

    R.sup.1 NHNH.sub.2

Formula XXIV

As used herein the term "halo" includes chloro, fluoro, bromo and iodo.Chloro is the preferred halo substituent because of the relatively lowcost and ease of preparation of the required chloro-substitutedintermediates and because the other halogens offer no particularadvantages over chloro. However, the other above-named halo substituentsare also satisfactory.

The term "dialkylamino in which alkyl is non-tertiary C₁ to C₄ alkyl"denotes saturated, acyclic groups which may be straight or branched asexemplified by dimethylamino, diethylamino, ethylmethylamino,dipropylamino, dibutylamino, isobutylmethyl and the like.

As used herein the terms "C₁ to C₃ alkyl", "non-tertiary C₁ to C₄alkyl", and "non-tertiary C₁ to C₁₆ alkyl" denote saturated monovalentstraight or branched aliphatic hydrocarbon radicals including methyl,ethyl, propyl, isopropyl, butyl, isobutyl, amyl, 1-methylbutyl,3-methylbutyl, hexyl, isohexyl, heptyl, isoheptyl, octyl, isooctyl,2-ethylhexyl, nonyl, 3-ethylheptyl, decyl, undecyl, dodecyl, tridecyl,1,3,5-trimethylhexyl, 1,5-dimethyl-4-ethylhexyl, 5-methyl-2-butylhexyl,2-propylnonyl, 2-butyloctyl, 2-pentanonyl, and the like.

The term "non-tertiary C₁ to C₄ alkoxy" includes saturated acyclic,straight or branched-chained groups as methoxy, ethoxy, propoxy,isopropoxy, butoxy, sec-butoxy, and isobutoxy.

As used herein, the term "C₂ to C₈ alkenyl" means monovalent aliphaticradicals possessing a single double bond, for example, ethenyl (orvinyl), 2-propenyl (or allyl), 1-methylethenyl or (isopropenyl),2-methyl-2-propenyl, 2-methyl-1-propenyl, 2-butenyl, 3-butenyl,1-pentenyl, 2-pentenyl, 3-methyl-2-butenyl, 2-methyl-1-butenyl(isoamylenyl), 3-methyl-1-butenyl, 1-hexenyl, 2-hexenyl, 3-hexenyl,2-heptenyl and 1-octenyl.

The compounds of Formulas I, VI, VII, XII, XVII and XVIII hereinaboveare essentially colorless in the depicted form. When contacted with anelectric current from an applied voltage stylus of the type ordinarilyemployed in electrochromic recording systems, the compounds of FormulasI, VI, VII, XII, XVII and XVIII develop yellow, yellow-brown,yellow-green, blue-green, blue, purple, magenta, and gray-coloredimages. These developed images are very insensitive to light, that is,once the color is developed it remains unchanged when subjected to lightexposure. The developed images also possess excellent xerographiccopiability.

The compounds of this invention may be incorporated in any of thecommercially-accepted systems known in the electrochromic recording art.Typical techniques for the application of the color formers to paper arewell-known and are described in numerous patents, for example, U.S. Pat.Nos. Re. 29,427; 3,726,769; 3,864,684; 3,871,972; 3,951,757; 4,017,366;and 4,133,933. The usual paper coatings consist of the color-formingcomponent, an organic metal salt, a binder and some type of conductor,either an inorganic salt or a conductive polymer. This mixture is milledtogether optionally in the presence of a non-ionic surface active agentuntil the desired particle size is obtained and then the mixture iscoated on paper and dried. Optionally, the color-forming substance canbe milled in the presence of a binder and the remaining componentsmilled also in the presence of a binder and the two mixtures combinedtogether prior to coating on paper. Normally the surface of the coatedpaper is wet with a conductive solution containing an inorganic alkalinemetal or alkaline earth metal salt, for example, potassium chloride,calcium chloride, sodium chloride, sodium bromide, potassium bromide,potassium nitrate or sodium sulfate immediately prior to the printingwith the applied voltage stylus. For a quick qualitative test, it hasbeen determined that the color-forming component can be dissolved in asuitable volatile organic solvent, coated on paper and the coated paperdried to obtain a paper sheet coated with the color-forming component.This coated sheet can then be wet with a conductive salt solution and animage traced with an applied voltage stylus to develop the coloredimage.

The compounds of Formulas I, VI, VII, XII, XVII and XVIII can be usedalone as color-forming components in electrochromic recording paper orcan be used in admixture with one or more other color-forming groups ofcompounds from the classes consisting of phthalides, for example,Crystal Violet Lactone; fluorans, for example,3-diethylamino-5,7-dimethylfluoran; redox indicators, for example,phenothiazines such as benzoyl leuco methylene blue and various othertypes of color-forming components currently employed incommercially-accepted electrochromic recording systems.

The best mode contemplated by the inventors of carrying out thisinvention will now be described so as to enable any person skilled inthe art to which it pertains to make and use the same.

In accordance with the aforementioned process aspects of this invention,the compounds of Formulas I, VI, VII, XII, XVII and XVIII are obtainedby reacting lactone compounds of Formulas XXIII, XXV and XXVI with a R¹substituted hydrazine of Formula XXIV. This reaction is convenientlycarried out in an appropriate inert organic liquid, for example, a loweralkyl alcohol such as ethanol or propanol; a glycol such as ethyleneglycol or propylene glycol; or a glycol ether such as ethoxyethanolcommonly known as the ethyl ether of ethylene glycol. Alternatively, thereaction can be run neat with excess hydrazine, for example,phenylhydrazine serving as the reaction medium. This reaction isconveniently carried out at a temperature in the range of 90° to 198°C., usually at the reflux temperature for periods of approximatelythirty minutes to approximately eighteen days. The compounds of FormulasI, VI, XII, XVII and XVIII thus obtained are isolated directly from thereaction medium after chilling. Alternatively, the desired product canbe isolated by pouring the reaction mixture into a mixture of ice andwater and filtering the resulting product. The isolated product can bepurified by conventional means such as recrystallization or reslurryingwith a suitable organic liquid followed by filtration. Alternatively,the purification can be combined with the isolation by extracting themixture of ice, water and product with a suitable water immiscibleorganic liquid, for example, toluene and then concentrating the organicliquid solution of the product by conventional means such as evaporationor distillation. In some instances, the compounds of Formulas I, VI andVII are insoluble in the reaction medium and are removed by filtration.The filtrate is then poured into a mixture of ice and water and thecompounds of Formulas XII, XVII and XVIII are isolated by filtration.

It will, of course, be appreciated that some of the starting phthalidesand furopyridinones are isomers and mixtures of isomers by virtue oftheir method of preparation as described in some of the patentsindicated hereinbelow. Throughout this application the nomenclature 5/6-is adopted in reference to 5/6-carboxyphthalides and esters thereof usedas starting materials to produce 6/7-carboxy-phthalazinones and estersthereof and 5/6-carboxyphthalimidines and esters thereof. Further, itwill be appreciated that the reaction of an inherently unsymmetricalanhydride in the preparation of the furopyridinones can produce isomersand mixtures of isomers. Since both isomers are useful in the practiceof this invention, the mixture of isomers formed was utilized as thestarting lactones in the practice of this invention.

The lactones of Formula XXIII, XXV and XXVI hereinabove, which arerequired as starting materials in the preparation of the final productsof Formulas I, VI, VII, XII, XVII and XVIII are generally knowngenerically as phthalides and furopyridinones. The following areexamples illustrative of a few of these lactones which can be utilizedin this invention: diaryl phthalides, for example,3,3-bis(4-dimethylaminophenyl)-6-dimethylaminophthalide commonly knownas crystal violet lactone, or simply CVL,3-(4-dimethylaminophenyl)-3-[2,4-bis(dimethylamino)phenyl]-6-dimethylaminophthalideand similar compounds described in U.S. Pat. No. 4,094,877 which issuedJune 13, 1978; aryl heteryl phthalides, for example,3-[2,4-bis(dimethylamino)phenyl]-3-(1-ethyl-2-methyl-3-indolyl)phthalidedisclosed in Belgian Pat. No. 864,376, granted Aug. 28, 1978, andsimilar compounds found in U.S. Pat. Nos. 3,491,112 and 4,153,609 whichissued Jan. 20, 1970 and May 8, 1979, respectively;bis(heteryl)phthalides, for example,3,3-bis(1-ethyl-2-methyl-3-indolyl)phthalide,3,3-bis(1-n-butyl-2-methyl-3-indolyl)phthalide and similar compoundsdescribed in U.S. Pat. Nos. 3,509,173 and 4,102,893 which issued Jan.20, 1970 and July 5, 1978, respectively;3-(2-ethoxy-4-diethylaminophenyl)-3-(1,2-dimethylindol-3-yl)-5/6-ethoxycarbonylphthalide and similar compounds described in U.S. Pat.No. 4,189,171 which issued Feb. 19, 1980; and furopyridinones, forexample,5/7-(2-methoxy-4-diethylaminophenyl)-5/7-(1-ethyl-2-methyl-3-indolyl)-furo[3,4b]-pyridine-5(7H)/7(5H)-one,described in Japanese Patent Publication 118,515/74, which publishedNov. 13, 1974.

The hydrazines and hydrazides of Formula XXIV constitute an old andwell-known class of compounds many of which are commercially-availableor are readily obtained by conventional syntheses well-known in the art.The following list exemplifies hydrazines useful in carrying out theprocess of this invention. Hydrazine, 2-aminophenylhydrazine,benzylhydrazine, 2-bromophenylhydrazine, 3-bromophenylhydrazine,4-bromophenylhydrazine, 2-chlorophenylhydrazine,3-chlorophenylhydrazine, 4-chlorophenylhydrazine,2,4-dichlorophenylhydrazine, 2,5-dichlorophenylhydrazine,2,6-dichlorophenylhydrazine, 3,4-dichlorophenylhydrazine,3,5-dichlorophenylhydrazine, 2,4-dinitrophenylhydrazine,4-methoxyphenylhydrazine, methylhydrazine, 2-nitrophenylhydrazine,3-nitrophenylhydrazine, 4-nitrophenylhydrazine, phenylhydrazine,2-methylphenylhydrazine, 3-methylphenylhydrazine,4-methylphenylhydrazine, methylhydrazinocarboxylate, acethydrazide,carbohydrazide, and pyridylhydrazine.

The molecular structures of the compounds of this invention wereassigned on the basis of the modes of synthesis and study of theirinfrared and nuclear magnetic resonance spectra.

The following examples will further illustrate the invention without,however, limiting it thereto. All melting points are uncorrected.

EXAMPLE 1

With stirring, a mixture of 1200.0 ml of 80 percent aqueous ethylalcohol, 25.0 g of3,3-bis(4-dimethylaminophenyl)-6-dimethylaminophthalide and 35.4 g of 85percent hydrazine hydrate was maintained at reflux temperature,approximately 90° C., for approximately three hours. After settingovernight at ambient temperature, the resulting slurry was chilled toapproximately 5° C. by means of an external ice bath. The solid wascollected by filtration, washed four times each with 50.0 ml of coldwater and air-dried to obtain 20.8 g of4,4-bis(4-dimethylaminophenyl)-7-dimethylaminophthalazin-1(2H)-one(Formula III: R=N(CH₃)₂ ; R¹ =R³ =R⁹ =H; R⁴ =R⁵ =R¹⁰ =R¹¹ =CH₃), awhite-colored solid which melted at 265°-270° C. Significant infraredmaxima appeared at 1660 cm⁻¹ (C=O;s) and 3400 cm⁻¹ (N-H;m). The nuclearmagnetic resonance spectrum was consistent with the assigned structure.Paper treated with an ink formulation of the product produced ablue-green-colored image when traced with an applied voltage stylus.

EXAMPLE 2

A mixture of 25.0 g of3,3-bis(4-dimethylaminophenyl)-6-dimethylaminophthalide, 300.0 ml ofethylene glycol and 35.4 g of 85 percent hydrazine hydrate wasmaintained at reflux temperature for approximately three days. Theresultant mixture was cooled to room temperature. The solid wascollected by filtration, washed with chilled ethyl alcohol and dried invacuo to obtain 8.4 g of a mixture of4,4-bis(4-dimethylaminophenyl)-7-dimethylaminophthalazin-1(2H)-one(Formula III: R=N(CH₃)₂ ; R¹ =R³ =R⁹ =H; R⁴ =R⁵ =R¹⁰ =R¹¹ =CH₃) and2-amino-3,3-bis(4-dimethylaminophenyl)-6-dimethylaminophthalimidine(Formula XIV: R=N(CH₃)₂ ; R¹ =R³ =R⁹ =H; R⁴ =R⁵ =R¹⁰ =R¹¹ =CH₃). Thefiltrate was added slowly with stirring to a mixture of ice and water.The solid which separated was collected by filtration, washed withchilled water and dried to obtain 10.1 g of2-amino-3,3-bis(4-dimethylaminophenyl)-6-dimethylaminophthalimidine(Formula XIV: R=N(CH₃)₂ ; R¹ =R³ =R⁹ =H; R⁴ =R⁵ =R¹⁰ =R¹¹ =CH₃), agreen-colored solid which melted at 133°-135° C. Significant infraredmaxima appeared at 3400 cm⁻¹ (N-H;m) and 1685 cm⁻¹ (C= O;s). The nuclearmagnetic resonance spectrum was in accord with the assigned structure.Paper treated with an ink formulation of the product produced ablue-colored image when traced with an applied voltage stylus.

EXAMPLE 3

A mixture of 25.0 g of3-(4-dimethylaminophenyl)-6-dimethylaminophthalide, 1700.0 ml of 40percent aqueous ethyl alcohol and 49.5 g of 85 percent hydrazine hydratewas maintained at reflux temperature with stirring for approximatelytwenty-four hours. The reaction mixture was cooled to ambienttemperature and slowly poured into a mixture of ice and water withstirring. The resulting solid was collected by filtration, washed withwater and dried to obtain 19.83 g of a mixture of4-(4-dimethylaminophenyl)-7-dimethylaminophthalazin-1(2H)-one (FormulaII: R=N(CH₃)₂ ; R¹ =R³ =Y=H; R⁴ =R⁵ =CH₃) and2-amino-3-(4-dimethylaminophenyl)-7-dimethylamminophthalimidine (FormulaXIII: R=N(CH₃)₂ ; R¹ =R³ =Y=H; R⁴ =R⁵ =CH₃), a solid which melted overthe range of 181.7°-189.4° C. The solid was suspended in warm ethylalcohol and stirred for approximately one-half hour. The solid wascollected by filtration, washed with a small amount of ethyl alcohol anddried to obtain 2.0 g of4-(4-dimethylaminophenyl)-7-dimethylaminophthalazin-1(2H)-one, a palegray-colored solid which melted at 230°-233° C. Infrared maxima appearedat 3215 cm⁻¹ (N-H;m) and 1667 cm⁻¹ (C=O;s). The nuclear magneticresonance spectrum was in accord with the assigned structure. Papertreated with an ink formulation of the product produced a gray-coloredimage when trace with an applied voltaage stylus. The ethyl alcoholfiltrate was poured slowly into water with stirring. The solid whichprecipitated was collected by filtration, washed with water and dried toobtain 16.0 g of2-amino-3-(4-dimethylaminophenyl)-6-dimethylaminophthalimidine, a paletan-colored solid which melted at 180°-181° C. Significant infraredmaxima appeared at 3440 cm⁻¹ (N-H;m) and 1685 cm⁻¹ (C=O;s). The nuclearmagnetic resonance spectrum was in accord with the assigned structure.Paper treated with an ink formulation of the product produced ablue-colored image.

EXAMPLE 4

A. With stirring, a mixture of 25.0 g of3,3-bis(1-butyl-2-methylindol-3-yl)phthalide, 300.0 ml of ethyleneglycol and 29.4 g of 85 percent hydrazine hydrate was maintained atreflux temperature approximately two days. After cooling to ambienttemperature, the resulting slurry was added slowly with stirring into amixture of ice and water. The solid was collected by filtration, washedwith water and dried in vacuo to obtain 21.7 g of2-amino-3,3-bis(1-butyl-2-methylindol-3-yl)phthalimidine (Formula XVI:R=R¹ =R⁸ =R¹⁴ =H; R⁶ =R¹² =C₄ H₉ ; R⁷ =R¹³ =CH₃), a yellow solid whichmelted at 103°-105° C. Infrared maxima appeared at 3440 cm⁻¹ (N-H;s),1690 cm⁻¹ (C=O;s) and 750 cm⁻¹ (indole;s). The nuclear magneticresonance spectrum was consistent with the assigned structure.

B. Four and one-half grams of the product from part A above wasdissolved in 150.0 ml of hot ethyl alcohol and the resulting solutionwas stirred for approximately thirty minutes with 1.0 g of decolorizingcharcoal. The carbon was removed by filtration and the filtrate wasconcentrated to approximately fifty milliliters by evaporation. To theresultant concentrate 200.0 ml of cyclohexane was added and the mixturewas cooled slowly. The solid which formed was collected by filtrationand dried to obtain 3.4 g of2-amino-3,3-bis(1-butyl-2-methylindol-3-yl)phthalimidine, a white solidwhich melted at 153°-154° C. Paper treated with an ink formulation ofthe product produced a purple-colored image when traced with an appliedvoltage stylus.

EXAMPLE 5

With stirring, a mixture of 25.0 g of3,3-bis(1-butyl-2-methylindol-3-yl)phthalide, 800.0 ml of ethyl alcohol,200.0 ml of water and 29.4 g of 85 percent hydrazine hydrate wasmaintained at reflux temperature for approximately forty-eight hours.The resulting mixture was chilled in an external ice bath to atemperature in the range of 0°-5° C. The solid was collected byfiltration, washed with chilled ethyl alcohol and dried in an air ovento obtain 23.65 g of4,4-bis(1-butyl-2-methylindol-3-yl)-phthalazin-1(2H)-one (Formula V:R=R¹ =R⁸ =R¹⁴ =H; R⁶ =R¹² =C₄ H₉ ; R⁷ =R¹³ =CH₃), a pale orange-coloredsolid which melted at 205.5°-206.5° C. In the infrared spectrum maximaappeared at 3400 cm⁻¹ (N-H;w) and 1670 cm⁻¹ (C=O;s). The nuclearmagnetic resonance spectrum was consistent with the assigned structure.Paper treated with an ink formulation of the product produced apurple-colored image when traced with an applied voltage stylus.

EXAMPLE 6

A. A mixture of 10.0 g of3,3-bis(4-dimethylaminophenyl)-6-dimethylaminophthalide and 26.0 g ofphenylhydrazine was maintained at a temperature in the range of140°-150° C. with stirring for approximately thirty hours. The solid wascollected by filtration, washed with toluene and air-dried to obtain 8.7g of a yellow solid. The solid was slurried in warm ethyl alcohol forapproximately one hour. The solid was collected by filtration and washedwith a small portion of ethyl alcohol. The alcohol filtrate was addedslowly to water with stirring. The solid which formed was collected byfiltration, washed with water and dried to obtain 4.2 g of2-anilino-3,3-bis(4-dimethylaminophenyl)-6-dimethylaminophthalimidine(Formula III: R=N(CH₃)₂ ; R¹ =C₆ H₅ ; R³ =R⁹ =H; R⁴ =R⁵ =R¹⁰ =R¹¹ =CH₃),a bright yellow solid which melted at 143°-145° C. Significant infraredmaxima appeared at 3420 cm⁻¹ (N-H;w) and 1700 cm⁻¹ (C=O;s). The nuclearmagnetic resonance spectrum was in accord with the assigned structure.

B. A mixture of 3.0 g of the product from A above and 30.0 ml of ethylalcohol was maintained at reflux temperature for approximately fifteenminutes. The solid was collected by filtering the hot mixture and waswashed first with 20.0 ml of hot ethyl alcohol and then with 20.0 ml ofroom temperature alcohol and dried to obtain 2.1 g of2-anilino-3,3-bis(4-dimethylaminophenyl)-6-dimethylaminophthalimidine, ayellow solid which melted over the range of 217°-222° C. Paper treatedwith an ink formulation containing the product produced a blue-coloredimage when traced with an applied voltage stylus.

EXAMPLE 7

With stirring a mixture of 10.0 g of3-(1-butyl-2-methylindol-3-yl)-3-(1-tetradecyl-2-methylindol-3-yl)phthalide,9.4 g of 85 percent hydrazine hydrate and 50.0 ml of 2-ethoxyethanol wasmaintained at approximately 100° C. for approximately two hours. Aftercooling the reaction mixture to approximately 50° C., there was addedslowly 75.0 ml of 5 percent aqueous ammonium hydroxide and 75.0 ml oftoluene and a small portion of saturated sodium chloride solution. Thewater layer was separated and extracted a second time with 75.0 ml offresh toluene. The two toluene portions were combined, washed withsaturated sodium chloride solution, and dried over anhydrous sodiumsulfate. The dried toluene layer was then concentrated under vacuum toobtain 11.5 g of4-(1-butyl-2-methylindol-3-yl)-4-(1-tetradecyl-2-methylindol-3-yl)phthalazin-1(2H)-one(Formula V: R=R¹ =R⁸ =R¹⁴ =H; R⁶ =C₄ H₉ ; R⁷ =R¹³ =CH₃ ; R¹² =C₁₄ H₂₉),a thick dark brown oil which upon standing turned into a wax-like solid.A significant infrared maximum appeared at 1668 cm⁻¹ (C=O;s). Thenuclear magnetic resonance spectrum was consistent with the assignedstructure. Paper treated with an ink formulation of the product produceda magenta-colored image when traced with an applied voltage stylus.

EXAMPLE 8

With stirring a mixture of 16.6 g of3,3-bis(4-dimethylaminophenyl)-6-(4-dimethylamino)phthalide and 9.0 g ofmethylhydrazinocarboxylate was maintained at 100°-110° C. forapproximately one hour and then maintained at approximately 150° C. forapproximately eighteen hours. The reaction mixture was maintained at175° C. for approximately one hour and at approximately 205° C. forapproximately twenty-one hours. The reaction mass was broken-up, addedto water and stirred at ambient temperature for approximately fourhours. After sitting overnight, the slurry was stirred an additional twohours and the solid was collected by filtration. The solid was dried invacuo obtaining 11.4 g of2-(methoxycarbonylamino)-3,3-bis(4-dimethylaminophenyl)-6-dimethylaminophthalimidine(Formula XIV: R=N(CH₃)₂ ; R¹ =CO₂ CH₃ ; R³ =R⁹ =H; R⁴ =R⁵ =R¹⁰ =R¹¹=CH₃), a brown-colored solid which melted at 98° C. with decomposition.A significant infrared maximum appeared at 1665 cm⁻¹ (C=O;s). Thenuclear magnetic resonance spectrum was in accord with the assignedstructure. Paper treated with an ink formulation of the product produceda blue-green-colored image when traced with an applied voltage stylus.

EXAMPLE 9

Following the procedure described in Example 8 above, a mixture of 12.5g of 3,3-bis(4-dimethylaminophenyl)-6-dimethylaminophthalide and 14.8 gof acethydrazide was maintained at approximately 140° C. forapproximately two and one-half hours, then at 160° C. for approximatelyeighteen hours and finally at approximately 180° C. for approximatelyninety minutes to obtain, after slurrying the reaction mass in water anddrying, 9.7 g of2-(acetylamino)-3,3-bis(4-dimethylaminophenyl)-6-dimethylaminophthalimidine(Formula XIV: R=N(CH₃)₂ ; R¹ =COCH₃ ; R³ =R⁹ =H; R⁴ =R⁵ =R¹⁰ =R¹¹ =CH₃),a pale white-colored solid which melted over the range 205°-215° C. Asignificant infrared maximum appeared at 1665 cm⁻¹ (C=O;m). The nuclearmagnetic resonance spectrum was concordant with the assigned structure.Paper treated with an ink formulation of the product produced ablue-colored image when traced with an applied voltage stylus.

EXAMPLE 10

Proceeding in a manner similar to that described in Example 8 above, amixture of 12.5 g of3,3-bis(4-dimethylaminophenyl)-6-dimethylaminophthalide and 9.0 g ofcarbohydrazide was maintained at approximately 180° C. for approximatelythirty-five hours to obtain, after reslurrying in water and drying, 9.8g of2-(hydrazinocarbonylamino)-3,3-bis(4-dimethylaminophenyl)-6-dimethylaminophthalimidine(Formula XIV: R=N(CH₃)₂ ; R¹ =CONHNH₂ ; R³ =R⁹ =H; R⁴ =R⁵ =R¹⁰ =R¹¹=CH₃), a brown-colored solid which melted at 221°-225° C. A significantinfrared maximum appeared at 1610 cm⁻¹ (C=O;s). The nuclear magneticresonance spectrum was in accord with the assigned structure. Papertreated with an ink formulation of the product produced a blue-coloredimage when traced with an applied voltage stylus.

Proceeding in a manner similar to that described in Example 3 above, theappropriate substituted phthalide or furopyridinone described in Column2 hereinbelow was interacted with hydrazine hydrate or other substitutedhydrazine in the organic medium given in Column 4 below at thetemperature of the mixture given in Column 5 for the period of timeindicated in Column 6 below. The product that was obtained is given inColumn 7 having the formula indicated in Column 8 with its physicalappearance in Column 9, its melting point in Column 10, significantinfrared maxima are indicated in Column 11 and its nuclear magneticresonance spectral analysis in Column 13 and the color produced when apaper sheet treated with an ink formulation containing the product wastraced with an applied voltage stylus is given in Column 14.

    TABLE A      Ex-             am-        Physical    Produced ple  Hydrazine Organic     Temper- Reaction  Product Appear- Melting Significant  Image No.     Starting Phthalide Hydrate Medium ature Time Product Formula ance Point     Infrared NMR Color       11 20.0 g 3-(4-Dimethylaminophenyl)- 24.1 g of 1114.0 ml of Reflux 28     hours 19.85 g 4-(4-Dimeth- III: R═N(CH.sub.3).sub.2 ; White 222.5-     3425 cm.sup.-1 Consistent Blue  3-(2-ethoxy-4-diethylaminophenyl)- 85     percent 40 percent   ylaminophenyl)-4-(2- R.sup.1 ═R.sup.9 ═H;     R.sup.3 ═ Powder 224.5° C. (N--H;m)  6-dimethylaminophthalide      ethyl alcohol   ethoxy-4-diethylamino- OC.sub.2 H.sub.5 ; R.sup.4     ═R.sup.5 ═   1670 cm.sup.-1       phenyl)-7-dimethyl- C.sub.2     H.sub.5 ; R.sup.10 ═R.sup.11      ═   (C═O;s)       aminophthalazin- CH.sub.3       1(2H)--one 12     15.0 g 3,3-Bis(4-dimethylamino- 23.5 g of 800.0 ml of Reflux 3 days 11.7     g 4,4-Bis(4-di- III: R═R.sup.1 ═R.sup.3 ═ Pale Green 203-     3390 cm.sup.-1 Consistent Blue-  phenyl)phthalide 85 percent 80 percent      methylaminophenyl)- R.sup.9 ═H; R.sup.4 ═R.sup.5 ═ Crystals     205.5° C. (N--H;m)  green    ethyl alcohol   phthalazin-1(2H)--     R.sup.10 ═R.sup.11 ═CH.sub.3   1665 cm.sup.-1       one     (C═O;s) 13 15.0 g 3-(4-Dimethylaminophenyl)- 21.2 g of 720.0 ml of     Reflux 5 days 8.6 g 4-(4-Dimethyl- III: R═R.sup.1 ═R.sup.9     ═H; Pale Tan 214° C. 3380 cm.sup.-1 Consistent Yellow-     3-[2,4-bis(dimethylamino)phenyl]- 85 percent 80 percent   aminophenyl)-4-     [2,4- R.sup.3 ═N(CH.sub.3).sub.2 ; R.sup.4 ═ Solid with de-     (N--H;m)  brown  phthalide  ethyl alcohol   bis(dimethylamino)- R.sup.5     ═R.sup.10 ═R.sup.11 ═CH.sub.3  composi- 1665 cm.sup.-1     phenyl]phthalazin-   tion (C═O;s)       1(2H)--one 16 20.0 g     3-(4-Dimethylaminophenyl)- 27.0 g of 920.0 ml of Reflux 48 hours 7.7 g     4-(4-Dimethyl- III: R═R.sup.3      ═ Tan 226- 3410 cm.sup.-1 Consistent Blue-  3-(1-butyl-2-methylindol     -3-yl)-6- 85 percent 80 percent   aminophenyl)-4-[2,4- N(CH.sub.3).sub.2     ; R.sup.1 ═ Powder 229°      C. (N--H;m)  green  dimethylaminophthalide  ethyl alcohol   bis(dimethyl     amino)- R.sup.9 ═H; R.sup.4 ═R.sup.5 ═   1666 cm.sup.-1      phenyl]-7-dimethyl- R.sup.11      ═CH.sub.3   (C═O;s)       aminophthalazin-       1(2H)--one 15     10.0 g 3,3-Bis(2-methyl-4-diethyl- 12.9 g of 440.0 ml of Reflux 18 days     1.6 g 4,4-Bis(2-Meth- III: R═R.sup.1 ═H; Pale Blue- 226.5- 3400     cm.sup.-1 Consistent Yellow  aminophenyl)phthalide 85 percent 80 percent       yl-4-dimethylamino- R.sup.3 ═R.sup.9 ═CH.sub.3 ; R.sup.4 ═     green 230° C. (N--H;m)    ethyl alcohol   phenyl)phthalazin-     R.sup.5 ═R.sup.10 ═R.sup.11 ═ Powder  1666 cm.sup.-1     1(2H)--one C.sub.2      H.sub.5   (C═O;s) 14 25.0 g 3-(4-Dimethylaminophenyl)- 31.8 g of     1200.0 ml of Reflux 96 hours 16.4 g 4-(4-Dimethyl- IV: R═N(CH.sub.3).     sub.2      ; Pale 153- 3370 cm.sup.-1 Consistent Blue-  3-[2,4-bis(dimethylamino)ph     enyl]- 85 percent 80 percent   aminophenyl)-4-(1- R.sup.1 ═R.sup.3     ═R.sup.14 ═H; Green 161°      C. (N--H;m)  green  6-dimethylaminophthalide  ethyl alcohol   butyl-2-me     thylindol- R.sup.4 ═R.sup.5 ═R.sup.13 ═CH.sub.3 ; Powder     1663 cm.sup.-1       3-yl)-7-dimethylamino- R.sup.12 ═C.sub.4     H.sub.9   (C═O;s)       phthalazin-1(2H)--    750 cm.sup.-1     one    (indole;s) 17 10.0 g 3-(2-Ethoxy-4-diethylamino- 11.8 g of 400.0     ml of Reflux 6 days 8.6 g 4-(2-Ethoxy-4- IV: R═R.sup.1 ═R.sup.14     ═H; White 200- 3300 cm.sup.-1 Consistent Yellow  phenyl)-3-(1-butyl-2     -methylindol-3- 85 percent 80 percent   diethylaminophenyl)-4- R.sup.3     ═OC.sub.2 H.sub.5 ; R.sup.4 ═ Powder 202° C. (N--H;m)     yl)phthalide  ethyl alcohol   (1-butyl-2-methyl- R.sup.5 ═C.sub.2     H.sub.5 ; R.sup.12 ═   1665 cm.sup.-1       indol-3-yl)phthalazin-     C.sub.4 H.sub.9 ; R.sup.13 ═CH.sub.3   (C═O;s)       1(2H)--one       750 cm.sup.-1           (indole;s) 18 25.0 g 3-(2-Ethoxy-4-diethylamino     - 30.6 g of 1040.0 ml of Reflux 24 hours 13.1 g 4-(2-Ethoxy-4- IV:     R═COOC.sub.2 H.sub.5 ; Pale 208- 3400 cm.sup.-1 Consistent Gray     phenyl)-3-(1-ethyl-2-methylindol-3- 85 percent 80 percent   diethylaminop     henyl)-4- R.sup.1 ═R.sup.14 ═H; R.sup.3 ═ Yellow 209°     C. (N--H;m)  yl)-5/6-ethoxycarbonylphthalide  ethyl alcohol   (1-ethyl-2-     methylindol- OC.sub.2 H.sub.5 ; R.sup.4 ═R.sup.5 ═ Powder  1670     cm.sup.-1       3-yl)-6/7-ethoxycarbon- R.sup.12 ═C.sub.2 H.sub.5 ;     R.sup.13 ═   (C═O;s)       yl-phthalazin-1(2H)-- CH.sub.3     one 19 10.0 g 3-(1,2-Dimethylindol-3-yl)- 11.2 g of 400.0 ml of Reflux 9     days 6.9 g 4-(1,2-Dimethyl- V: R═COOC.sub.2 H.sub.5 ; Orange 103-     3400 cm.sup.-1 Consistent Purple  3-(1-ethyl-2-methylindol-3-yl)-5/6- 85     percent 80 percent   indol-3-yl)-4-(1-ethyl- R.sup.1 ═R.sup.8     ═R.sup.14 ═H; Powder 105.5°      C. (N--H;m)  ethoxycarbonylphthalide  ethyl alcohol   2-methylindol-3-yl     )- R.sup.6 ═C.sub.2 H.sub.5 ; R.sup.7 ═   1670 cm.sup.-1     6/7-ethoxycarbonyl- R.sup.12 ═R.sup.13 ═CH.sub.3   (C═O;s)         phthalazin-1(2H)--one    750 cm.sup.-1           (indole;s) 20 5.1 g     3,3-Bis(1-ethyl-2-methyl- 5.0 ml of 60.0 ml of Reflux 22/3 hours 1.3 g     4,4-Bis(1-ethyl- V: R═COOCH.sub.3 ; White 227-  Consistent Magenta     indol-3-yl)-5/6-methoxycarbonyl- 85 percent methyl alcohol   2-methylindo     l-3-yl)- R.sup.1 ═R.sup.8 ═R.sup.14 ═H; Solid 230° C.      phthalide  35.0 ml of   6/7-methoxycarbonyl- R.sup.6 ═R.sup.12     ═C.sub.2 H.sub.5 ;    ethyl alcohol   phthalazin-1(2H)--one R.sup.7     ═R.sup.13 ═CH.sub.3 21 25.0 g 3-(1-Ethyl-2-methylindol-3- 30.6 g     of 1040.0 ml of Reflux 48 hours 14.9 g 4-(1-ethyl-2- V: R═R.sup.1     ═R.sup.8 ═ Pale 186.5- 3370 cm.sup.-1 Consistent Purple     yl)-3-(1-butyl-2-methylindol-3-yl)- 85 percent 80 percent   methylindol-3     -yl)-4- R.sup.14 ═H; R.sup.6 ═ Orange 193° C. (N--H;m)     phthalide  ethyl alcohol   (1-butyl-2-methylindol- C.sub.2 H.sub.5 ;     R.sup.12 ═C.sub.4 H.sub.9      ; Powder  1665 cm.sup.-1       3-yl)phthalazin- R.sup.7 ═R.sup.13     ═CH.sub.3   (C═O;s)       1(2H)--one    750 cm.sup.-1     (indole;s) 22 20.0 g Of an isomeric mixture of 24.7 g of 850.0 ml of     Reflux 6 days 16.5 g Of an isomeric VIII & IX: Pale 215- 3300 cm.sup.-1     Consistent Yellow-  7-(2-ethoxy-4-diethylaminophenyl)- 85 percent 80     percent   mixture of 8-(2-ethoxy- R═R.sup.1 ═R.sup.14 ═H;     Tan 219° C. (N--H;m)  green  7-(1-ethyl-2-methylindol-3-yl)-     ethyl alcohol   4-diethylaminophenyl)- R.sup.3 ═OC.sub.2 H.sub.5 ;     R.sup.4 ═ Powder  1670 cm.sup.-1  furo-[3,4b]-pyridine-5(7H)--one     and     8-(1-ethyl-2-methyl- R.sup.5 ═R.sup.12 ═C.sub.2 H.sub.5     ;   (C═O;s)  5-(2-ethoxy-4-diethylaminophenyl)-     indol-3-yl)-pyrid     o- R.sup.13      ═CH.sub.3   750 cm.sup.-1  5-(1-ethyl-2-methylindol-3-yl)-furo-     [2,3d]-pyridazin-5(6H)--    (indole;s)  (3,4b)-pyridine-7(5H)--one     one and 5-(2-ethoxy-4-       diethylaminophenyl)-5-       (1-ethyl-2-meth     ylindol-       3-yl)-pyrido-[2,3d]-       pyridazin-8(5H)--one 23 25.0 g     Of an isomeric mixture of 32.5 g of 1100.0 ml of Reflux 6 days 20.5 g Of     an isomeric VIII & IX: Pale 242.5- 3415 cm.sup.-1 Consistent Purple     7-[2,4-bis(dimethylamino)phenyl]- 85 percent 80 percent   mixture of     8-[2,4-bis- R═R.sup.1 ═R.sup.14 ═H; Gray 246° C. (N--     H;m)  7-(1-ethyl-2-methylindol-3-yl)-  ethyl alcohol   (dimethylamino)phe     nyl]- R.sup.3 ═N(CH.sub.3).sub.2      ; Powder  1669 cm.sup.-1  furo-[3,4b]-pyridine-5(7H)--one and     8-(1-ethyl-2-methyl- R.sup.4 ═R.sup.5 ═R.sup.13 ═CH.sub.3 ;      (C═O;s)  5-[2,4-bis(dimethylamino)phenyl]-5-     indol-3-yl)-pyrido-      R.sup.12 ═C.sub.2      H.sub.5   752 cm.sup.-1  (1-ethyl-2-methylindol-3-yl)-furo-     [2,3d]-pyridazine-5(6H)--    (indole;s)  [3,4b]-pyridine-7(5H)--one     one and 5-[2,4-bis(di-       methylamino)phenyl]-5-       (1-ethyl-2-meth     ylindol-       3-yl)-pyrido-[2,3d]-       pyridazin-8(5H)--one

Following a procedure similar to that described in Example 7 above, theappropriate substituted phthalide described in Column 2 hereinbelow wasinteracted with the appropriate hydrazine given in Column 3 below in theorganic medium given in Column 4 below at the temperature of the mixturegiven in Column 5 for the period of time indicated in Column 6 below.The product that was obtained is given in Column 7 having the formulaindicated in Column 8 with its physical appearance described in Column9, its melting point in Column 10, significant infrared maxima of theproduct is given in Column 11, its nuclear magnetic resonance spectralanalysis indicated in Column 13 and the color produced when a papersheet coated with an ink formulation containing the product was tracedwith an applied voltage stylus is given in Column 14.

    TABLE B      Ex-             am-        Physical    Produced ple  Hydrazine Organic     Temper- Reaction  Product Appear- Melting Significant  Image No.     Starting Phthalide Hydrate Medium ature Time Product Formula ance Point     Infrared NMR Color       24 10.0 g 3-(1-Octyl-2-methylindol-3- 9.4 g of 100.0 ml 2- 100°     C. 6 hours 7.5 g 4-(1-Octyl-2- V: R═R.sup.1 ═R.sup.8 ═ White 1     72- 1665 cm.sup.-1 Consistent Magenta  yl)-3-(1-phenoxyethyl-2-methyl-     85 percent Ethoxyethanol   methylindol-3-yl)-4- R.sup.14 ═H; R.sup.6     ═C.sub.8 H.sub.17 ; Powder 174°      C. (C═O;s)  indol-3-yl)phthalide     (1-phenoxyethyl-2- R.sup.7     ═R.sup.13 ═CH.sub.3 ; R.sup.12 ═       methylindol-3-yl)-     C.sub.6 H.sub.5 OC.sub.2 H.sub.4       phthalazin-1(2H)--one 25 5.0 g     3,3-Bis(1-phenoxyethyl-2-4.7 g of 50.0 ml 2- 100° C. 20 hours 1.0     g 4,4-Bis(1- V: R═R.sup.1 ═R.sup.8 ═ White 119- 3420     cm.sup.-1 Consistent Magenta  methylindol-3-yl)phthalide 85 percent     Ethoxyethanol   phenoxyethyl-2-meth- R.sup.14 ═H; R.sup.6      ═R.sup.12 ═ Powder 122° C. (N--H;s)       ylindol-3-yl)-     C.sub.6 H.sub.5 OC.sub.2 H.sub.4 ; R.sup.7 ═   1617 cm.sup.-1     phthalazin-1(2H)-- R.sup.13 ═CH.sub.3   (C═O;s)       one 26     25.0 g 3-(1-Butyl-2-methylindol-3- 30.6 g of 300.0 ml 175° C. 15     minutes 21.8 g 2-Amino-3-(1- XVI: R═R.sup.1 ═R.sup.8 ═ White     220- 3440 cm.sup.-1 Consistent Purple  yl)-3-(1-ethyl-2-methylindol-3-yl)     - 85 percent Ethylene   butyl-2-methylindol- R.sup.14 ═H; R.sup.6     ═C.sub.8 H.sub.17 ; Powder 221° C. (N--H;m)  phthalide     Glycol   3-yl)-3-(1-ethyl-2- R.sup.7 ═R.sup.13 ═CH.sub.3 ;     R.sup.12 ═   1690 cm.sup.-1       methylindol-3-yl)- C.sub.2 H.sub.5       (C═O;s)       phthalimidine 27 5.0 g 3-(1-Benzyl-2-methylindol-3-     5.8 g of 75.0 ml 2- 100° C. 15 hours 2.4 g 4-(1-Benzyl-2- V:     R═R.sup.1 ═R.sup.8 ═ Yellow 211- 3400 cm.sup.-1 Consistent     Purple  yl)-3-(1-ethyl-2-methylindol-3-yl)- 85 percent Ethoxyethanol     methylindol-3-yl)-4- R.sup.14 ═H; R.sup.6 ═ Powder 213°     C. (N--H;s)  phthalide     (1-ethyl-2-methyl- C.sub.6 H.sub.5 CH.sub.2 ;     R.sup.7 ═R.sup.13 ═   1670 cm.sup.-1       indol-3-yl)- CH.sub.3     ; R.sup.12 ═C.sub.2 H.sub.5   (C═O;s)       phthalazin-1(2H)--         one 28 10.0 g 3-(1-Benzyl-2-methylindol-3- 10.0 g of 150.0 ml 2-     100° C. 7 hours 6.4 g 4-(1-Benzyl-2- V: R═R.sup.1      ═R.sup.8 ═ Pale 155- 3420 cm.sup.-1 Consistent Magenta     yl)-3-(1-octyl-2-methylindol-3-yl)- 85 percent Ethoxyethanol   methylindo     l-3-yl)-4- R.sup.14 ═H; R.sup.6 ═ Orange 165° C. (N--H;s)      phthalide     (1-octyl-2-methyl- C.sub.6 H.sub.5 CH.sub.2 ; R.sup.7     ═R.sup.13 ═ Powder  1667 cm.sup.-1       indol-3-yl)-phtha-     CH.sub.3 ; R.sup.12 ═C.sub.8      H.sub.17   (C═O;s)       lazin-1(2H)--one 29 5.0 g 3,3-Bis(4-dimethy     laminophen- 13.1 g of 2- (none) 155°      C. 24 hours 2.2 g 2-(2-Pyridyl- XIV: R═N(CH.sub.3).sub.2 ; Tan 198-     3440 cm.sup.-1 Consistent Blue  yl)-6-dimethylaminophthalide Hydrazino-       amino)-3,3-bis(4- R.sup.1 ═2-pyridyl- Powder 202° C.     (N--H;s)   pyridine    dimethylaminophen- amino; R.sup.3 ═R.sup.9     ═H;   1710 cm.sup.-1       yl)-6-dimethylamino- R.sup.4 ═R.sup.5     ═R.sup.10 ═R.sup.11 ═   (C═O;s)       phthalimidine     CH.sub.3 30 3.0 g 3-(1-Benzyl-2-methylindol-3- 2.0 ml of 20.0 ml     40° C. 18 hours 2.1 g A mixture of V & XVI: R═ Pale 110- 3400     cm.sup.-1 Consistent Purple  yl)-3-(1-octyl-2-methylindol-3-yl)- 85     percent N,N--di-   4-(1-benzyl-2-meth- (Cl).sub.4 ; R.sup.1 ═R.sup.8     ═ Brown 113.5° C. (N--H;s)  4,5,6,7-tetrachlorophthalide     methyl-   ylindol-3-yl)-4-(1- R.sup.14 ═H; R.sup.6 ═ Powder     1740 cm.sup.-1    formamide   octyl-2-methylindol- C.sub.6 H.sub.5     CH.sub.2 ; R.sup.7 ═R.sup.13      ═   (C═O;s)       3-yl)-5,6,7,8-tetra- CH.sub.3 ; R.sup.12     ═C.sub.8 H.sub.17       chlorophthalazin-       1(2H)--one and 2-        amino-3-(1-benzyl-2-       methylindol-3-yl)-3-       (1-octyl-2-methy     l-       indol-3-yl)-4,5,6,7-       tetrachlorophthali-       midine

Following a procedure similar to that described in Example 4 above, theappropriate substituted phthalide or furopyridinone described in Column2 hereinbelow was interacted with hydrazine hydrate in the organicmedium given in Column 4 below at the temperature of the mixture givenin Column 5 for the period of time indicated in Column 6 below. Theproduct that was obtained is given in Column 7 having the formulaindicated in Column 8 with its physical appearance described in Column9, its melting point in Column 10, significant infrared maxima of theproduct is given in Column 11, its nuclear magnetic resonance spectralanalysis indicated in Column 13 and the color produced when a papersheet coated with an ink formulation containing the product was tracedwith an applied voltage stylus is given in Column 14.

    TABLE C      Ex-             am-        Physical    Produced ple  Hydrazine Organic     Temper- Reaction  Product Appear- Melting Significant  Image No.     Starting Phthalide Hydrate Medium ature Time Product Formula ance Point     Infrared NMR Color       31 10.0 g 3-(4-Dimethylaminophenyl)- 12.9 g of 150.0 ml 2- 105°     C. 2 hours 10.1 g 4-(4-Dimethyl- IV: R═N(CH.sub.3).sub.2 ; Tan 208-     3400 cm.sup.-1 Consistent Blue-  3-(1-ethyl-2-methylindol-3-yl)-6- 85     percent Ethoxy-   aminophenyl)-4-(1- R.sup.1 ═R.sup.3 ═R.sup.14     ═H; Solid 212° C. (N--H;m)  green  dimethylaminophthalide     ethanol   ethyl-2-methylindol- R.sup.4 ═R.sup.5 ═R.sup.13     ═CH.sub.3 ;   1660 cm.sup.-1       3-yl)-7-dimethyl- R.sup.12     ═C.sub.2 H.sub.5   (C═O;s)       aminophthalazin-    750     cm.sup.-1       1(2H)--one    (indole;s) 32 20.0 g 3-(2-Ethoxy-4-diethyla     mino- 24.1 g of 200.0 ml 2- Reflux 2 hours 18.7 g 4-(2-Ethoxy- IV:     R═R.sup.1 ═R.sup.14 ═ White 223.5- 3420 cm.sup.-1 Consistent     Gray  phenyl)-3-(1-ethyl-2-methylindol- 85 percent Ethoxy-   4-diethylami     nophen- H; R.sup.3 ═OC.sub.2 H.sub.5 ; Powder 225° C.     (N--H;m)  3-yl)phthalide  ethanol   yl)-4-(1-ethyl-2- R.sup.4      ═R.sup.5 ═R.sup.12      ═   1665 cm.sup.-1       methylindol-3-yl)- C.sub.2 H.sub.5 ;     R.sup.13 ═CH.sub.3   (C═O;s)       phthalazin-1(2H)--    750     cm.sup.-1       one    (indole;s) 33 25.0 g 3-(2-Ethoxy-4-diethylamino-     27.6 g of 300.0 ml 2- 100° C. 1 hour 3.7 g 4-(2-Ethoxy-4- IV:     R═R.sup.1 ═R.sup.14 ═ Pale 172- 3350 cm.sup.-1 Consistent     Yellow-  phenyl)-3-(1-ethyl-2-methylindol- 85 percent Ethoxy-   diethylam     inophenyl)- H; R.sup.3 ═OC.sub.2 H.sub.5 ; Tan 175° C.     (N--H;m)  brown  3-yl)-5/6-carboxyphthalide  ethanol   4-(1-ethyl-2-methy     l- R.sup.4 ═R.sup.5 ═R.sup.12 ═ Solid  1670 cm.sup.-1     indol-3-yl)phthal- C.sub.2 H.sub.5 ; R.sup.13      ═CH.sub.3   (C═O;s)       azin-1(2H)--one    750 cm.sup.-1     (indole;s) 34 25.0 g 3,3-Bis(1-ethyl-2-methyl- 32.9 g of Ethylene Reflux     30 23.4 g 3,3-Bis(1- XVI: R═R.sup.1      ═ White 143.5- 3430 cm.sup.-1 Consistent Magenta  indol-3-yl)phthali     de 85 percent glycol  minutes ethyl-2-methylindol- R.sup.8 ═R.sup.14     ═H; Powder 145° C. (N--H;m)       3-yl)phthalimidine R.sup.6     ═R.sup.12 ═C.sub.2 H.sub.5 ;   1690 cm.sup.-1        R.sup.7     ═R.sup.13 ═CH.sub.3   (C═O;s)           750 cm.sup.-1        (indole;s) 35 5.0 g Of an isomeric mixture of 6.5 g of 50.0 ml 2-     100° C. 6 hours 4.3 g Of an isomeric X & XI: R═ Pale 201-     3410 cm.sup.-1 Consistent Purple  7,7-bis(1-ethyl-2-methylindol-3- 85     percent Ethoxy-   mixture of 8,8-bis(1- R.sup.1 ═R.sup.8      ═R.sup.14 ═H; Yellow 203.5°      C. (N--H;m)  yl)-furo-[3,4b]-pyridine-5[7H]--one  ethanol   ethyl-2-meth     ylindol- R.sup.6 ═R.sup.12 ═C.sub.2 H.sub.5 ; Solid  1672     cm.sup.-1  and 5,5-bis(1-ethyl-2-methylindol-     3-yl)-pyrido-[2,3d]-     R.sup.7 ═R.sup.13      ═CH.sub.3   (C═O;s)  3-yl)-furo-[3,4b]-pyridine-7[5H]--one     pyridazin-5(6H)--one    750 cm.sup.-1       and 5,5-bis(1-ethyl-     (indole;s)       2-methylindol-3-yl)-       pyrido-[2,3d]-pyri-     dazin-8(5H)--one 36 10.0 g 3-(1-Octyl-2-methylindol-3- 10.0 g of 150.0     ml 100° C. 6 hours 6.4 g 4-(1-Octyl-2- V: R═R.sup.1      ═R.sup.8 ═ Pale 155- 3420 cm.sup.-1 Consistent Magenta     yl)-3-(1-benzyl-2-methylindol-3-yl)- 85 percent Ethoxy-   methylindol-3-y     l)-4- R.sup.14 ═H; R.sup.6 ═C.sub.8 H.sub.17      ; Orange 165°      C. (N--H;s)  phthalide  ethanol   (1-benzyl-2-methyl- R.sup.7      ═R.sup.13 ═CH.sub.3      ; Solid  1667 cm.sup.-1       indol-3-yl)-phtha- R.sup.12 ═C.sub.6     H.sub.5 CH.sub.2   (C═O;s)       lazin-1(2H)--one    750 cm.sup.-1             (indole;s) 37 15.0 g 3-(4-Dimethylaminophenyl)-3- 17.6 g of     225.0 ml 100° C. 2 hours 13.0 g Of a mixture III & IV: R═     Pale 80- 3420 cm.sup.-1 Consistent Blue  (4-N--ethyl-N--benzylaminophenyl     )-6- 85 percent Ethoxy-   of 4-(4-dimethyl- N(CH.sub.3).sub.2 ; R.sup.1     ═ Blue- 92° C. (N--H;m)  dimethylaminophthalide  ethanol     aminophenyl)-4-(4-N-- R.sup.3 ═R.sup.9 ═H; R.sup.4 ═ green     1670 cm.sup.-1       ethyl-N--benzylamino- R.sup.5 ═R.sup.10     ═R.sup.11 ═CH.sub.3 Solid  (C═O;m)       phenyl)-7-dimethyl-           aminophthalazin-       1(2H)--one and 3-(4-       dimethylaminophen     yl)-       3-(4-N--ethyl-N--benz-       ylaminophenyl)-6-di-     methylaminophthalimi-       dine

It is contemplated that by following the procedure described in theforegoing examples but employing the appropriate 3-(2-R³ -4-N-R⁴ -N-R⁵-aminophenyl-5/6-R-phthalides with the appropriate R¹ -substitutedhydrazine of Formula XXIV, there will be obtained 3-R¹ -4-[2-R³ -4-(N-R⁴-N-R⁵ -amino)phenyl]-R-phthalazin-1(2H)-ones of Formula II wherein Y ishydrogen, presented in Examples 38-49, presented in Table D hereinbelow.

                                      TABLE D                                     __________________________________________________________________________    Example No.                                                                          R      R.sup.1  R.sup.3   R.sup.4                                                                          R.sup.5                                   __________________________________________________________________________    38     N(C.sub.2 H.sub.5).sub.2                                                             2-ClC.sub.6 H.sub.4                                                                    CH.sub.3 O                                                                              C.sub.3 H.sub.7                                                                  C.sub.3 H.sub.7                           39     COOC.sub.4 H.sub.9                                                                   4-Cl--2CH.sub.3 C.sub.6 H.sub.3                                                        H         C.sub.4 H.sub.9                                                                  C.sub.4 H.sub.9                           40     (Cl).sub.4                                                                           4-CH.sub.3 OC.sub.6 H.sub.4                                                            C.sub.4 H.sub.9 O                                                                       CH.sub.3                                                                         CH.sub.3                                  41     COOC.sub.8 H.sub.17                                                                  3-NO.sub.2 C.sub.6 H.sub.4                                                             C.sub.2 H.sub.5 O                                                                       C.sub.2 H.sub.5                                                                  C.sub.2 H.sub.5                           42     N(C.sub.4 H.sub.9).sub.2                                                             4-CH.sub.3 C.sub.6 H.sub.4                                                             C.sub.3 H.sub.7                                                                         CH.sub.3                                                                         CH.sub.3                                  43     COOC.sub.3 H.sub.7                                                                   H        H         C.sub.2 H.sub.5                                                                  C.sub.6 H.sub.5 CH.sub.2                  44     COOC.sub.16 H.sub.33                                                                 2,3-(NO.sub.2).sub.2 C.sub.6 H.sub.3                                                   H         C.sub.2 H.sub.5                                                                  C.sub.2 H.sub.5                           45     COOC.sub.12 H.sub.25                                                                 3-BrC.sub.6 H.sub.4                                                                    H         CH.sub.3                                                                         CH.sub.3                                  46     N(C.sub.3 H.sub.7).sub.2                                                             3,4-(Cl).sub.2 C.sub.6 H.sub.3                                                         C.sub. 3 H.sub.7 O                                                                      C.sub.2 H.sub.5                                                                  C.sub.2 H.sub.5                           47     H      3-NO.sub.2 C.sub.6 H.sub.4                                                             N(C.sub.4 H.sub.9).sub.2                                                                C.sub.4 H.sub.9                                                                  C.sub.4 H.sub.9                           48     COOC.sub.6 H.sub.13                                                                  4-BrC.sub.6 H.sub.4                                                                    C.sub.2 H.sub.5 CONH                                                                    CH.sub.3                                                                         CH.sub.3                                  49     N(CH.sub.3).sub.2                                                                    H        N(C.sub.2 H.sub.5)(C.sub.6 H.sub.5 CH.sub.2)                                            C.sub.2 H.sub.5                                                                  C.sub.6 H.sub.5 CH.sub.2                  __________________________________________________________________________

It is contemplated that by following the procedure described in theforegoing examples but employing the appropriate 3-[2-R³ -4-(N-R⁴ -N-R⁵-amino)phenyl]-3-[2-R⁹ -4-(N-R¹⁰ -N-R¹¹ -amino)phenyl]-5/6-R-phthalideswith the appropriate R¹ -substituted hydrazine of Formula XXIV, therewill be obtained 3-R¹ -4-[2-R³ -4-(N-R⁴ -N-R⁵ -amino)phenyl]-4-[2-R³-4-(N-R⁴ -N-R⁵ -amino)phenyl]-R-phthalazin-1(2H)-ones of Formula III,presented in Examples 50-61, presented in Table E hereinbelow.

                                      TABLE E                                     __________________________________________________________________________           Part 1                         Part 2                                  Example No.                                                                          R       R.sup.1   R.sup.3   R.sup.4                                                                          R.sup.5                                                                             R.sup.9 R.sup.10                                                                         R.sup.11               __________________________________________________________________________    50     N(C.sub.2 H.sub.5).sub.2                                                              2-ClC.sub.6 H.sub.4                                                                     CH.sub.3 O                                                                              C.sub.3 H.sub.7                                                                  C.sub.3 H.sub.7                                                                     H       C.sub.2 H.sub.5                                                                  4-CH.sub.3 C.sub.6                                                            H.sub.3 CH.sub.2       51     COOC.sub.4 H.sub.9                                                                    4-Cl--2CH.sub.3 C.sub.6 H.sub.3                                                         H         C.sub.4 H.sub.9                                                                  C.sub.4 H.sub.9                                                                     C.sub.3 H.sub.7 O                                                                     C.sub.2 H.sub.5                                                                  C.sub.2 H.sub.5        52     H       4-CH.sub.3 OC.sub.6 H.sub.4                                                             C.sub.4 H.sub.9 O                                                                       CH.sub.3                                                                         CH.sub.3                                                                            H       C.sub.4 H.sub.9                                                                  C.sub.4 H.sub.9        53     COOC.sub.8 H.sub.17                                                                   3-NO.sub.2 C.sub.6 H.sub.4                                                              C.sub.2 H.sub.5 O                                                                       C.sub.2 H.sub.5                                                                  C.sub.2 H.sub.5                                                                     C.sub.2 H.sub.5 CONH                                                                  CH.sub.3                                                                         CH.sub.3               54     N(C.sub.4 H.sub.9).sub.2                                                              4-CH.sub.3 C.sub.6 H.sub.4                                                              C.sub.3 H.sub.7                                                                         CH.sub.3                                                                         CH.sub.3                                                                            C.sub.2 H.sub.5                                                                       C.sub.3 H.sub.7                                                                  C.sub.3 H.sub.7        55     COOC.sub.3 H.sub.7                                                                    H         H         C.sub.2 H.sub.5                                                                  C.sub.6 H.sub.5 CH.sub.2                                                            H       CH.sub.3                                                                         4-ClC.sub.6                                                                   H.sub.4 CH.sub.2       56     COOC.sub.16 H.sub.33                                                                  2,4-(NO.sub.2).sub.2 C.sub.6 H.sub.3                                                    H         C.sub.2 H.sub.5                                                                  C.sub.2 H.sub.5                                                                     H       C.sub.2 H.sub.5                                                                  C.sub.2 H.sub.5        57     COOC.sub.12 H.sub.25                                                                  3-BrC.sub.6 H.sub.4                                                                     H         CH.sub.3                                                                         CH.sub.3                                                                            N(CH.sub.3).sub.2                                                                     CH.sub.3                                                                         CH.sub.3               58     N(C.sub.3 H.sub.7).sub.2                                                              3,4-(Cl).sub.2 C.sub.6 H.sub.3                                                          C.sub.3 H.sub.7 O                                                                       C.sub.2 H.sub.5                                                                  C.sub.2 H.sub.5                                                                     C.sub.3 H.sub.7 CONH                                                                  C.sub.2 H.sub.5                                                                  C.sub.2 H.sub.5        59     (Br).sub.4                                                                            3-NO.sub.2 C.sub.6 H.sub.4                                                              N(C.sub.4 H.sub.9).sub.2                                                                C.sub.4 H.sub.9                                                                  C.sub.4 H.sub.9                                                                     C.sub.4 H.sub.9 O                                                                     CH.sub.3                                                                         CH.sub.3               60     COOC.sub.6 H.sub.13                                                                   4-BrC.sub.6 H.sub.4                                                                     C.sub.2 H.sub.5 CONH                                                                    CH.sub.3                                                                         CH.sub.3                                                                            CH.sub.3 O                                                                            C.sub.4 H.sub.9                                                                  C.sub.4 H.sub.9        61     N(CH.sub.3).sub.2                                                                     H         N(C.sub.2 H.sub.5)(C.sub.6 H.sub.5 CH.sub.2)                                            C.sub.2 H.sub.5                                                                  C.sub.6 H.sub.5 CH.sub.2                                                            H       C.sub.2 H.sub.5                                                                  C.sub.2 H.sub.5        __________________________________________________________________________

It is contemplated that by following the procedure described in theforegoing examples but employing the appropriate 3-[2-R³ -4-(N-R⁴ -N-R⁵-amino)phenyl]-3-(1-R¹² -2-R¹³ -5/6-R¹⁴ -indol-3-yl)-5/6-R-phthalideswith the appropriate R¹ -substituted hydrazine of Formula XXIV, therewill be obtained 3-R¹ -4-[2-R³ -4-(N-R⁴ -N-R⁵ -amino)phenyl]-4-(1-R¹²-2-R¹³ -5/6-R¹⁴ -indol-3-yl)-R-phthalazin-1(2H)-one of Formula IV,presented in Examples 62-73, presented in Table F hereinbelow.

                                      TABLE F                                     __________________________________________________________________________           Part 1                   Part 2                                        Example No.                                                                          R       R.sup.1                                                                              R.sup.3                                                                              R.sup.4                                                                          R.sup.5 R.sup.12                                                                             R.sup.13                                                                         R.sup.14                    __________________________________________________________________________    62     N(C.sub.4 H.sub.9).sub.2                                                              2-BrC.sub.6 H.sub.9                                                                  C.sub.4 H.sub.9 CONH                                                                 C.sub.2 H.sub.5                                                                  C.sub.2 H.sub.5                                                                       C.sub.6 H.sub.5 CH.sub.2                                                             CH.sub.3                                                                         H                           63     COOC.sub.4 H.sub.9                                                                    2-NH.sub.2 C.sub.6 H.sub.4                                                           H      C.sub.2 H.sub.5                                                                  C.sub.6 H.sub.5 CH.sub.2                                                              C.sub.8 H.sub.17                                                                     C.sub.2 H.sub.5                                                                  H                           64     COOC.sub.12 H.sub.25                                                                  2-ClC.sub.6 H.sub.4                                                                  C.sub.2 H.sub.5 O                                                                    C.sub.4 H.sub.9                                                                  C.sub.4 H.sub.9                                                                       C.sub.6 H.sub.13                                                                     C.sub.6 H.sub.5                                                                  5-CH.sub.3                  65     N(C.sub.3 H.sub.7).sub.2                                                              3,5-Cl.sub.2 C.sub.6 H.sub.3                                                         C.sub.3 H.sub.7 CONH                                                                 CH.sub.3                                                                         CH.sub.3                                                                              C.sub.16 H.sub.33                                                                    C.sub.2 H.sub.5                                                                  5-CH.sub.3                  66     N(C.sub.2 H.sub.5).sub.2                                                              3-ClC.sub.6 H.sub.4                                                                  C.sub.4 H.sub.9 O                                                                    CH.sub.3                                                                         4-CH.sub.3 C.sub.6 H.sub.4                                                            C.sub. 12 H.sub.25                                                                   C.sub.2 H.sub.5                                                                  5-Br, 6-NO.sub.2            67     COOC.sub.6 H.sub.13                                                                   CH.sub.3                                                                             N(CH.sub.3).sub.2                                                                    CH.sub.3                                                                         CH.sub.3                                                                              CH.sub.3 CHCH                                                                        CH.sub.3                                                                         6-Br                        68     COOC.sub.10 H.sub.21                                                                  2,6-Cl.sub.2 C.sub.6 H.sub.3                                                         H      C.sub.2 H.sub.5                                                                  4-CH.sub.3 C.sub.6 H.sub.4 CH.sub.2                                                   CH.sub.3                                                                             CH.sub.3                                                                         6-NO.sub.2                  69     COOH    H      C.sub.3 H.sub.7 O                                                                    C.sub.2 H.sub.5                                                                  C.sub.2 H.sub.5                                                                       C.sub.4 H.sub.9                                                                      H  5-CH.sub.3 O                70     N(CH.sub.3).sub.2                                                                     4-BrC.sub.6 H.sub.4                                                                  N(C.sub.2 H.sub.5).sub.2                                                             C.sub.2 H.sub.5                                                                  C.sub.2 H.sub.5                                                                       C.sub.6 H.sub.13                                                                     C.sub.6 H.sub.5                                                                  6-Cl                        71     (Cl).sub.2                                                                            4-NO.sub.2 C.sub.6 H.sub.4                                                           C.sub.4 H.sub.9 O                                                                    C.sub.2 H.sub.5                                                                  4-ClC.sub.6 H.sub.4 CH.sub.2                                                          CH.sub.3                                                                             C.sub.3 H.sub.7                                                                  H                           72     COOCH.sub.3                                                                           3-CH.sub.3 C.sub.6 H.sub.4                                                           H      CH.sub.3                                                                         CH.sub.3                                                                              CH.sub.2 CH                                                                          CH.sub.3                                                                         H                           73     COOHC.sub.16 H.sub.33                                                                 H      CH.sub.3 O                                                                           C.sub.4 H.sub.9                                                                  C.sub.4 H.sub.9                                                                       2-FC.sub.6 H.sub.4 CH.sub.2                                                          CH.sub.3                                                                         H                           __________________________________________________________________________

It is contemplated that by following the procedure described in theforegoing examples but employing the appropriate 3-(1-R⁶ -2-R⁷ -5/6-R⁸-indol-3-yl)-3-(1-R¹² -2-R¹³ -5/6-R¹⁴ -indol-3-yl)-5/6-R-phthalides withthe appropriate R¹ -substituted hydrazine of Formula XXIV, there will beobtained 3-R¹ -4-(1-R⁶ -2-R⁷ -5/6-R⁸ -indol-3-yl)-4-(1-R¹² -2-R¹³-5/6-R¹⁴ -indol-3-yl)-R-phthalazin-1(2H)-one of Formula V, presented inExamples 74-85, presented in Table G hereinbelow.

                                      TABLE G                                     __________________________________________________________________________           Part 1                  Part 2                                         Example No.                                                                          R      R.sup.1                                                                              R.sup.6                                                                              R.sup.7                                                                          R.sup.8                                                                              R.sup.12 R.sup.13                                                                         R.sup.14                    __________________________________________________________________________    74     N(C.sub.2 H.sub.5).sub.2                                                             2-CH.sub.3 C.sub.6 H.sub.4                                                           C.sub.3 H.sub.7                                                                      C.sub.6 H.sub.5                                                                  6-Cl   3-ClC.sub.6 H.sub.4 CH.sub.2                                                           C.sub.2 H.sub.5                                                                  H                           75     N(C.sub.4 H.sub.9).sub.2                                                             3-BrC.sub.6 H.sub.4                                                                  2-FC.sub.6 H.sub.4 CH.sub.2                                                          CH.sub.3                                                                         H      C.sub.8 H.sub.17                                                                       CH.sub.3                                                                         H                           76     COOC.sub.6 H.sub.13                                                                  2-NH.sub.2 C.sub.6 H.sub.4                                                           C.sub.4 H.sub.9                                                                      H  5,6-(CH.sub.3 O).sub.2                                                               C.sub.5 H.sub.11                                                                       H  H                           77     COOC.sub.16 H.sub.33                                                                 H      C.sub.6 H.sub.5 CH.sub.2                                                             H  6-F    C.sub.2 H.sub.5                                                                        CH.sub.3                                                                         5,6-(CH.sub.3).sub.2        78     H      3,4-Cl.sub.2 C.sub.6 H.sub.3                                                         H      C.sub.2 H.sub.5                                                                  H      4-ClC.sub.6 H.sub.4 CH.sub.2                                                           CH.sub.3                                                                         5-NO.sub.2                  79     COOH   4-CH.sub.3 OC.sub.6 H.sub.4                                                          CH.sub.3                                                                             CH.sub.3                                                                         5-NO.sub.2                                                                           C.sub.4 H.sub.9                                                                        H  5-CH.sub.3 O                80     COOC.sub.8 H.sub.17                                                                  4-CH.sub.3 C.sub.6 H.sub.4                                                           C.sub.6 H.sub.5 OC.sub.2 H.sub.4                                                     C.sub.2 H.sub.5                                                                  5-CH.sub.3                                                                           CH.sub.2 CH                                                                            CH.sub.3                                                                         H                           81     N(C.sub.3 H.sub.7).sub.2                                                             4-NO.sub.2 C.sub.6 H.sub.4                                                           C.sub.6 H.sub.13                                                                     H  H      2,6-Cl.sub.2 C.sub.6 H.sub.3                                                  CH.sub.2 CH.sub.3                                                                         H                           82     N(C.sub.2 H.sub.5).sub.2                                                             H      H      C.sub.6 H.sub.5                                                                  6-Cl   C.sub.6 H.sub.5 CH.sub.2                                                               H  5-Cl                        83     N(C.sub.4 H.sub.9).sub.2                                                             CH.sub.3                                                                             CH.sub.3 CHCH                                                                        CH.sub.2                                                                         H      C.sub.16 H.sub.33                                                                      CH.sub.3                                                                         H                           84     COOC.sub.12 H.sub.25                                                                 C.sub.6 H.sub.5                                                                      CH.sub.3                                                                             H  5-Br, 6-NO.sub.2                                                                     C.sub.2 H.sub.5                                                                        C.sub.3 H.sub.7                                                                  H                           85     COOCH.sub.3                                                                          2-ClC.sub.6 H.sub.4                                                                  C.sub.8 H.sub.17                                                                     H  5-I    C.sub.2 H.sub.5                                                                        CH.sub.3                                                                         5,6-(CH.sub.3).sub.2        __________________________________________________________________________

It is contemplated that by following the procedure described in theforegoing examples but employing the appropriate 3-[2-R³ -4-(N-R⁴ -N-R⁵-amino)phenyl]-3-[2-R⁹ -4-(N-R¹⁰ -N-R¹¹ -amino)phenyl]-5/6-R-phthalideswith the appropriate R¹ -substituted hydrazine of Formula XXIV, therewill be obtained 2-(R¹ -amino)-3-[2-R² -4-(N-R⁴ -N-R⁵-amino)phenyl]-3-[2-R⁹ -4-(N-R¹⁰ -N-R¹¹ -amino)phenyl]-6-R-phthalimidineof Formula XVI, presented in Examples 86-97, presented in Table Hhereinbelow.

                                      TABLE H                                     __________________________________________________________________________           Part 1                         Part 2                                  Example No.                                                                          R       R.sup.1   R.sup.3   R.sup.4                                                                          R.sup.5                                                                            R.sup.9 R.sup.10                                                                         R.sup.11                __________________________________________________________________________    86     N(C.sub.2 H.sub.5).sub.2                                                              2-ClC.sub.6 H.sub.4                                                                     CH.sub.3 O                                                                              C.sub.3 H.sub.7                                                                  C.sub.3 H.sub.7                                                                    H       C.sub.2 H.sub.5                                                                  4-CH.sub.3 C.sub.6                                                            H.sub.4 CH.sub.2        87     COOC.sub.4 H.sub.9                                                                    4-Cl--2-CH.sub.3 C.sub.6 H.sub.3                                                        H         C.sub.4 H.sub.9                                                                  C.sub.4 H.sub.9                                                                    C.sub.3 H.sub.7 O                                                                     C.sub.2 H.sub.5                                                                  C.sub.2 H.sub.5         88     (Cl).sub.4                                                                            4-CH.sub.3 OC.sub.6 H.sub.4                                                             C.sub.4 H.sub.9 O                                                                       CH.sub.3                                                                         CH.sub.3                                                                           H       C.sub.4 H.sub.9                                                                  C.sub.4 H.sub.9         89     COOC.sub.8 H.sub.17                                                                   3-NO.sub.2 C.sub.6 H.sub.4                                                              C.sub.2 H.sub.5 O                                                                       C.sub.2 H.sub.5                                                                  C.sub.2 H.sub.5                                                                    C.sub.2 H.sub.5 CONH                                                                  CH.sub.3                                                                         CH.sub.3                90     N(C.sub.4 H.sub.9).sub.2                                                              4-CH.sub.3 C.sub.6 H.sub.4                                                              C.sub.3 H.sub.7                                                                         CH.sub.3                                                                         CH.sub.3                                                                           C.sub.2 H.sub.5 O                                                                     C.sub.3 H.sub.7                                                                  C.sub.3 H.sub.7         91     COOC.sub.3 H.sub.7                                                                    H         H         C.sub.2 H.sub.5                                                                  C.sub.6 H.sub.5 CH.sub.2                                                           H       CH.sub.3                                                                         4-ClC.sub.6 H.sub.4                                                           CH.sub.2                92     COOC.sub.16 H.sub.33                                                                  2,4-(NO.sub.2).sub.2 C.sub.6 H.sub.3                                                    H         C.sub.2 H.sub.5                                                                  C.sub.2 H.sub.5                                                                    H       C.sub.2 H.sub.5                                                                  C.sub.2 H.sub.5         93     COOC.sub.12 H.sub.25                                                                  3-BrC.sub.6 H.sub.4                                                                     H         CH.sub.3                                                                         CH.sub.3                                                                           N(CH.sub.3).sub.2                                                                     CH.sub.3                                                                         CH.sub.3                94     N(C.sub.3 H.sub.7).sub.2                                                              3,4-(Cl).sub.2 C.sub.6 H.sub.3                                                          C.sub.3 H.sub.7 O                                                                       C.sub.2 H.sub.5                                                                  C.sub.2 H.sub.5                                                                    C.sub.3 H.sub.7 CONH                                                                  C.sub.2 H.sub.5                                                                  C.sub.2 H.sub.5         95     H       3-NO.sub.2 C.sub.6 H.sub.4                                                              N(C.sub.4 H.sub.9).sub.2                                                                C.sub.4 H.sub.9                                                                  C.sub.4 H.sub.9                                                                    C.sub.4 N.sub.9 O                                                                     CH.sub.3                                                                         CH.sub.3                96     COOC.sub.6 H.sub.13                                                                   4-BrC.sub.6 H.sub.4                                                                     C.sub.2 H.sub.5 CONH                                                                    CH.sub.3                                                                         CH.sub.3                                                                           CH.sub.3 O                                                                            C.sub.4 H.sub.9                                                                  C.sub.4 H.sub.9         97     N(CH.sub.3).sub.2                                                                     H         N(C.sub.2 H.sub.5)(C.sub. 6 H.sub.5 CH.sub.2)                                           C.sub.2 H.sub.5                                                                  C.sub.6 H.sub.5 CH.sub.2                                                           H       C.sub.2 H.sub.5                                                                  C.sub.2 H.sub.5         __________________________________________________________________________

It is contemplated that by following the procedure described in theforegoing examples but employing the appropriate 3-[2-R³ -4-(N-R⁴ -N-R⁵-amino)phenyl]-3-(1-R¹² -2-R¹³ -5/6-R¹⁴ -indol-3-yl)-5/6-R-phthalideswith the appropriate R¹ -substituted hydrazine of Formula XXIV, therewill be obtained 2-(R¹ -amino)-3-[2-R³ -4-(N-R⁴ -N-R⁵-amino)pheny]-3-(1-R¹² -2-R¹³ -5/6-R¹⁴ -indol-3-yl)-6-R-phthalimidine ofFormula XV, presented in Examples 98-109, presented in Table Ihereinbelow.

                                      TABLE I                                     __________________________________________________________________________           Part 1                   Part 2                                        Example No.                                                                          R       R.sup.1                                                                              R.sup.3                                                                              R.sup.4                                                                          R.sup.5 R.sup.12                                                                             R.sup.13                                                                         R.sup.14                    __________________________________________________________________________     98    N(C.sub.4 H.sub.9).sub.2                                                              2-BrC.sub.6 H.sub.4                                                                  C.sub.4 H.sub.9 CONH                                                                 C.sub.2 H.sub.5                                                                  C.sub.2 H.sub.5                                                                       C.sub.6 H.sub.5 CH.sub.2                                                             CH.sub.3                                                                         H                            99    COOC.sub.4 H.sub.9                                                                    2-NH.sub.2 C.sub.6 H.sub.4                                                           H      C.sub.2 H.sub.5                                                                  C.sub.6 H.sub.5 CH.sub.2                                                              C.sub.8 H.sub.17                                                                     C.sub.2 H.sub.5                                                                  H                           100    COOC.sub.12 H.sub.25                                                                  2-ClC.sub.6 H.sub.4                                                                  C.sub.2 H.sub.5 O                                                                    C.sub.4 H.sub.9                                                                  C.sub.4 H.sub.9                                                                       C.sub.6 H.sub.13                                                                     C.sub.6 H.sub.5                                                                  5-CH.sub.3                  101    N(C.sub.3 H.sub.7).sub.2                                                              3,5-Cl.sub.2 C.sub.6 H.sub.3                                                         C.sub.3 H.sub.7 CONH                                                                 CH.sub.3                                                                         CH.sub.3                                                                              C.sub.16 H.sub.33                                                                    C.sub.2 H.sub.5                                                                  5-CH.sub.3                  102    N(C.sub.2 H.sub.5).sub.2                                                              3-ClC.sub.6 H.sub.3                                                                  C.sub.4 H.sub.9 O                                                                    CH.sub.3                                                                         4-CH.sub.3 C.sub.6 H.sub.4                                                            C.sub.12 H.sub.25                                                                    C.sub.2 H.sub.5                                                                  5-Br, 6-NO.sub.2            103    COOC.sub.6 H.sub.13                                                                   CH.sub.3                                                                             N(CH.sub.3).sub.2                                                                    CH.sub.3                                                                         CH.sub.3                                                                              CH.sub.3 CHCH                                                                        CH.sub.3                                                                         6-Br                        104    COOC.sub.10 H.sub.21                                                                  2,6-Cl.sub.2 C.sub.6 H.sub.3                                                         H      C.sub.2 H.sub.5                                                                  4-CH.sub.3 C.sub.6 H.sub.4 CH.sub.2                                                   CH.sub.3                                                                             CH.sub.3                                                                         6-NO.sub.2                  105    COOH    H      C.sub.3 H.sub.7 O                                                                    C.sub.2 H.sub.5                                                                  C.sub.2 H.sub.5                                                                       C.sub.4 H.sub.9                                                                      H  5-CH.sub.3 O                106    N(CH.sub.3).sub.2                                                                     4-BrC.sub.6 H.sub.4                                                                  N(C.sub.2 H.sub.5).sub.2                                                             C.sub.2 H.sub.5                                                                  C.sub.2 H.sub.5                                                                       C.sub.6 H.sub.13                                                                     C.sub.6 H.sub.5                                                                  6-Cl                        107    H       4-NO.sub.2 C.sub.6 H.sub.4                                                           C.sub.4 H.sub.9 O                                                                    C.sub.2 H.sub.5                                                                  4-ClC.sub.6 H.sub.4 CH.sub.2                                                          CH.sub.3                                                                             C.sub.3 H.sub.7                                                                  H                           108    COOCH.sub.3                                                                           3-CH.sub.3 C.sub.6 H.sub.4                                                           H      CH.sub.3                                                                         CH.sub.3                                                                              CH.sub.2 CH                                                                          CH.sub.3                                                                         H                           109    COOHC.sub.16 H.sub.33                                                                 H      CH.sub.3 O                                                                           C.sub.4 H.sub.9                                                                  C.sub.4 H.sub.9                                                                       2-FC.sub.6 H.sub.4 CH.sub.2                                                          CH.sub.3                                                                         H                           __________________________________________________________________________

It is contemplated that by following the procedure described in theforegoing examples but employing the appropriate 3-(1-R⁶ -2-R⁷ -5/6-R⁸-indol-3-yl)-3-(1-R¹² -2-R¹³ -5/6-R¹⁴ -indol-3-yl)-5/6-R-phthalides withthe appropriate R¹ -substituted hydrazine of Formula XXIV, there will beobtained 2-(R¹ -amino)-3-(1-R⁶ -2-R⁷ -5/6-R⁸ -indol-3-yl)-3-(1-R¹²-2-R¹³ -5/6-R¹⁴ -indol-3-yl)-6-R-phthalimidine of Formula XVI, presentedin Examples 110-121, presented in Table J hereinbelow.

                                      TABLE J                                     __________________________________________________________________________           Part 1                  Part 2                                         Example No.                                                                          R      R.sup.1                                                                              R.sup.6                                                                              R.sup.7                                                                          R.sup.8                                                                              R.sup.12 R.sup.13                                                                         R.sup.14                    __________________________________________________________________________    110    N(C.sub.2 H.sub.5).sub.2                                                             2-CH.sub.3 C.sub.6 H.sub.4                                                           C.sub.3 H.sub.7                                                                      C.sub.6 H.sub.5                                                                  6-Cl   3-ClC.sub.6 H.sub.4 CH.sub.2                                                           C.sub.2 H.sub.5                                                                  H                           111    N(C.sub.4 H.sub.9).sub.2                                                             3-BrC.sub.6 H.sub.4                                                                  2-FC.sub.6 H.sub.4 CH.sub.2                                                          CH.sub.3                                                                         H      C.sub.8 H.sub.17                                                                       CH.sub.3                                                                         H                           112    COOC.sub.6 H.sub.13                                                                  2-NH.sub.2 C.sub.6 H.sub.4                                                           C.sub.4 H.sub.9                                                                      H  5,6-(CH.sub.3 O).sub.2                                                               C.sub.5 H.sub.11                                                                       H  H                           113    COOC.sub.16 H.sub.33                                                                 H      C.sub.6 H.sub.5 CH.sub.2                                                             H  6-F    C.sub.2 H.sub.5                                                                        CH.sub.3                                                                         5,6-(CH.sub.3).sub.2        114    (Cl).sub.4                                                                           3,4-Cl.sub.2 C.sub.6 H.sub.3                                                         H      C.sub.2 H.sub.5                                                                  H      4-ClC.sub.6 H.sub.4 CH.sub.2                                                           CH.sub.3                                                                         5-NO.sub.2                  115    COOH   4-CH.sub.3 OC.sub.6 H.sub.4                                                          CH.sub.3                                                                             CH.sub.3                                                                         5-NO.sub.2                                                                           C.sub.4 H.sub.9                                                                        H  5-CH.sub.3 O                116    COOC.sub.8 H.sub.17                                                                  4-CH.sub.3 C.sub.6 H.sub.4                                                           C.sub.4 H.sub.9                                                                      C.sub.2 H.sub.5                                                                  5-CH.sub.3                                                                           CH.sub.2 CH                                                                            CH.sub.3                                                                         H                           117    N(C.sub.3 H.sub.7).sub.2                                                             4-NO.sub.2 C.sub.6 H.sub.4                                                           C.sub.6 H.sub.13                                                                     H  H      2,6-Cl.sub.2 C.sub.6 H.sub.3                                                  CH.sub.2 CH.sub.3                                                                         H                           118    N(C.sub.2 H.sub.5).sub.2                                                             H      H      C.sub.6 H.sub.5                                                                  6-Cl   C.sub.6 H.sub.5 CH.sub.2                                                               H  5-Cl                        119    N(C.sub.4 H.sub.9).sub.2                                                             CH.sub.3                                                                             CH.sub.3 CHCH                                                                        CH.sub.3                                                                         H      C.sub.16 H.sub.33                                                                      CH.sub.3                                                                         H                           120    COOC.sub.12 H.sub.25                                                                 C.sub.6 H.sub.5                                                                      CH.sub.3                                                                             H  5-Br, 6-NO.sub.2                                                                     C.sub.2 H.sub.5                                                                        C.sub.3 H.sub.7                                                                  H                           121    COOCH.sub.3                                                                          2-ClC.sub.6 H.sub.4                                                                  C.sub.8 H.sub.17                                                                     H  5-I    C.sub.2 H.sub.5                                                                        CH.sub.3                                                                         5,6-(CH.sub.3).sub.2        __________________________________________________________________________

It is contemplated that by following the procedure described in theforegoing examples but employing the appropriate isomeric mixture of7-[2-R³ -4-(N-R⁴ -N-R⁵ -amino)-phenyl]-7-(1-R¹² -2-R¹³ -5/6-R¹⁴-indol-3-yl)-furo-(3,4b)-pyridine-5(7H)-one and 5-[2-R³ -4-(N-R⁴ -N-R⁵-amino)phenyl]-5-(1-R¹² -2-R¹³ -5/6-R¹⁴-indolyl)-(3,4b)-pyridine-7(5H)-one with the appropriate R¹ -substitutedhydrazine of Formula XXIV, there will be obtained an isomeric mixture ofR¹ -8-[2-R³ -4-(N-R⁴ -N-R⁵ -amino)phenyl]-7-(1-R¹² -2-R¹³ -5/6-R¹⁴-indol-3-yl)pyrido-[2,3d]-pyridazin-5(6H)-ones and R-5-[2-R³ -4-(N-R⁴-N-R⁵ -amino)phenyl]-5-(1-R¹² -2-R¹³ -R¹⁴ -indol-3-yl)-6-R¹-pyrido-[2,3d]-pyridazin-8(5H)-ones of Formulas VIII and IX, presentedin Examples 122-133, presented in Table K hereinbelow.

                                      TABLE K                                     __________________________________________________________________________           Part 1           Part 2                                                Example No.                                                                          R.sup.1                                                                              R.sup.3                                                                              R.sup.4                                                                          R.sup.5 R.sup.12                                                                             R.sup.13                                                                         R.sup.14                            __________________________________________________________________________    122    2-BrC.sub.6 H.sub.4                                                                  C.sub.4 H.sub.9 CONH                                                                 C.sub.2 H.sub.5                                                                  C.sub.2 H.sub.5                                                                       C.sub.6 H.sub.5 CH.sub.2                                                             CH.sub.3                                                                         H                                   123    2-NH.sub.2 C.sub.6 H.sub.4                                                           H      C.sub.2 H.sub.5                                                                  C.sub.6 H.sub.5 CH.sub.2                                                              C.sub.8 H.sub.17                                                                     C.sub.2 H.sub.5                                                                  H                                   124    2-ClC.sub.6 H.sub.4                                                                  C.sub.2 H.sub.5 O                                                                    C.sub.4 H.sub.9                                                                  C.sub.4 H.sub.9                                                                       C.sub.6 H.sub.13                                                                     C.sub.6 H.sub.5                                                                  5-CH.sub.3                          125    3,5-Cl.sub.2 C.sub.6 H.sub.3                                                         C.sub.3 H.sub.7 CONH                                                                 CH.sub.3                                                                         CH.sub.3                                                                              C.sub.16 H.sub.33                                                                    C.sub.2 H.sub.5                                                                  5-CH.sub.3                          126    3-ClC.sub.6 H.sub.3                                                                  C.sub.4 H.sub.9 O                                                                    CH.sub.3                                                                         4-CH.sub.3 C.sub.6 H.sub.4 CH.sub.2                                                   C.sub.12 H.sub.25                                                                    C.sub.2 H.sub.5                                                                  5-Br, 6-NO.sub.2                    127    CH.sub.3                                                                             N(CH.sub.3).sub.2                                                                    CH.sub.3                                                                         CH.sub.3                                                                              CH.sub.3 CHCH                                                                        CH.sub.3                                                                         6-Br                                128    2,6-Cl.sub.2 C.sub.6 H.sub.3                                                         H      C.sub.2 H.sub.5                                                                  4-CH.sub.3 C.sub.6 H.sub.4 CH.sub.2                                                   CH.sub.3                                                                             CH.sub.3                                                                         6-NO.sub.2                          129    H      C.sub.3 H.sub.7 O                                                                    C.sub.2 H.sub.5                                                                  C.sub.2 H.sub.5                                                                       C.sub.4 H.sub.9                                                                      H  5-CH.sub.3 O                        130    4-BrC.sub.6 H.sub.4                                                                  N(C.sub.2 H.sub.5).sub.2                                                             C.sub.2 H.sub.5                                                                  C.sub.2 H.sub.5                                                                       C.sub.6 H.sub.13                                                                     C.sub.6 H.sub.5                                                                  6-Cl                                131    4-NO.sub.2 C.sub.6 H.sub.4                                                           C.sub.4 H.sub.9 O                                                                    C.sub.2 H.sub.5                                                                  4-ClC.sub.6 H.sub.4 CH.sub.2                                                          CH.sub.3                                                                             C.sub.3 H.sub.7                                                                  H                                   132    3-CH.sub.3 C.sub.6 H.sub.4                                                           H      CH.sub.3                                                                         CH.sub.3                                                                              CH.sub.2 CH                                                                          CH.sub.3                                                                         H                                   133    H      CH.sub.3 O                                                                           C.sub.4 H.sub.9                                                                  C.sub.4 H.sub.9                                                                       2-FC.sub.6 H.sub.4 CH.sub.2                                                          CH.sub.3                                                                         H                                   __________________________________________________________________________

It is contemplated that by following the procedure described in theforegoing examples but employing the appropriate isomeric mixture of7-(1-R⁶ -2-R⁷ -5/6-R⁸ -indol-3-yl)-7-(1-R¹² -2-R¹³ -5/6-R¹⁴-indol-3-yl)-furo-(3,4b)-pyridin-5(7H)-one and 5-(1-R⁶ -2-R⁷ -5/6-R⁸-indol-3-yl)-5-(1-R¹² -2-R¹³ -5/6-R¹⁴ -indolyl)-(3,4b)-pyridin-7(5H)-onewith the appropriate R¹ -substituted hydrazine of Formula XXIV, therewill be obtained an isomeric mixture of 2/3-R-7-R¹ -8-(1-R⁶ -2-R⁷-5/6-R⁸ -indol-3-yl)-8-(1-R¹² -2-R¹³ -5/6-R¹⁴-indol-3-yl)pyrido-[2,3d]-pyridazin-5(6H)-ones and 5-(1-R⁶ -2-R⁷ -5/6-R⁸-indol-3-yl)-5-(1-R¹² -2-R¹³ -3-R¹⁴ -indol-3-yl)-6-R¹-pyrido-[2,3d]-pyridazin-8(5H)-ones of Formulas X and XI, presented inTable L hereinbelow.

                                      TABLE L                                     __________________________________________________________________________           Part 1                  Part 2                                         Example No.                                                                          R.sup.1                                                                              R.sup.6                                                                              R.sup.7                                                                          R.sup.8                                                                              R.sup.12                                                                              R.sup.13                                                                         R.sup.14                            __________________________________________________________________________    134    2-CH.sub.3 C.sub.6 H.sub.4                                                           C.sub.3 H.sub.7                                                                      C.sub.6 H.sub.5                                                                  6-Cl   3-ClC.sub.6 H.sub.4 CH.sub.2                                                          C.sub.2 H.sub.5                                                                  H                                   135    3-BrC.sub.6 H.sub.4                                                                  2-FC.sub.6 H.sub.4 CH.sub.2                                                          CH.sub.3                                                                         H      C.sub.8 H.sub.17                                                                      CH.sub.3                                                                         H                                   136    2-NH.sub.2 C.sub.6 H.sub.4                                                           C.sub.4 H.sub.9                                                                      H  5,6-(CH.sub.3 O).sub.2                                                               C.sub.5 H.sub.11                                                                      H  H                                   137    H      C.sub.6 H.sub.5 CH.sub.2                                                             H  6-F    C.sub.2 H.sub.5                                                                       CH.sub.3                                                                         5,6-(CH.sub.3).sub.2                138    3,4-Cl.sub.2 C.sub.6 H.sub.3                                                         H      C.sub.2 H.sub.5                                                                  H      4-ClC.sub.6 H.sub.4 CH.sub.2                                                          CH.sub.3                                                                         5-NO.sub.2                          139    4-CH.sub.3 OC.sub.6 H.sub.4                                                          CH.sub.3                                                                             CH.sub.3                                                                         5-NO.sub.2                                                                           C.sub.4 H.sub.9                                                                       H  5-CH.sub.3 O                        140    4-CH.sub.3 C.sub.6 H.sub.4                                                           C.sub.4 H.sub.9                                                                      C.sub.2 H.sub.5                                                                  5-CH.sub.3                                                                           CH.sub.2 CH                                                                           CH.sub.3                                                                         H                                   141    4-NO.sub.2 C.sub.6 H.sub.4                                                           C.sub.6 H.sub.13                                                                     H  H      6-Cl.sub.2 C.sub.6 H.sub.3 CH.sub.2                                                   CH.sub.3                                                                         H                                   142    H      H      C.sub.6 H.sub.5                                                                  6-Cl   C.sub.6 H.sub.5 CH.sub.2                                                              H  5-Cl                                143    CH.sub.3                                                                             CH.sub.3 CHCH                                                                        CH.sub.3                                                                         H      C.sub.16 H.sub.33                                                                     CH.sub.3                                                                         H                                   144    C.sub.6 H.sub.5                                                                      CH.sub.3                                                                             H  5-Br, 6-NO.sub.2                                                                     C.sub.2 H.sub.5                                                                       C.sub.3 H.sub.7                                                                  H                                   145    2-ClC.sub.6 H.sub.4                                                                  C.sub.8 H.sub.17                                                                     H  5-I    C.sub.2 H.sub.5                                                                       CH.sub.3                                                                         5,6-(CH.sub.3).sub.2                __________________________________________________________________________

What is claimed is:
 1. A substrate for use in electrochromic recordingcomprising a support sheet containing as a color-forming substance a3-R¹ -4-X-4-Y-R-phthalazin-1(2H)-one having the structural formula##STR57## wherein: R represents hydrogen, dialkylamino in which alkyl isnon-tertiary C₁ to C₄ alkyl, COOR² in which R² is hydrogen ornon-tertiary C₁ to C₁₆ alkyl or one to four halo;R¹ represents hydrogen,C₁ to C₃ alkyl, pyridyl, ##STR58## in which Z is non-tertiary C₁ to C₄alkoxy, NHNH₂, or non-tertiary C₁ to C₄ alkyl, phenyl or phenylsubstituted by one or two of C₁ to C₃ alkyl, non-tertiary C₁ to C₄alkoxy, halo, nitro or amino; X is selected from the group consisting of##STR59## Y is selected from the group consisting of hydrogen, ##STR60##in which R³ and R⁹ independently represent hydrogen, non-tertiary C₁ toC₄ alkyl, non-tertiary C₁ to C₄ alkoxy, acylamido in which acyl isnon-tertiary C₂ to C₄ alkyl or dialkylamino in which alkyl isnon-tertiary C₁ to C₄ alkyl, R⁴ and R¹⁰ independently representnon-tertiary C₁ to C₄ alkyl, benzyl or benzyl substituted in the benzenering by one or two of halo or C₁ to C₃ alkyl, R⁵ and R¹¹ independentlyrepresent non-tertiary C₁ to C₄ alkyl, benzyl or benzyl substituted inthe benzene ring by one or two of halo or C₁ to C₃ alkyl, R⁶ and R¹²independently represent hydrogen, non-tertiary C₁ to C₁₆ alkyl,non-tertiary C₂ to C₈ alkylene, phenoxyethyl, benzyl or benzylsubstituted in the benzene ring by one or two of halo or C₁ to C₃ alkyl,R⁷ and R¹³ independently represent hydrogen, C₁ to C₃ alkyl or phenyl,and R⁸ and R¹⁴ independently represent hydrogen, halo, non-tertiary C₁to C₄ alkyl, non-tertiary C₁ to C₄ alkoxy or nitro.
 2. A substrate foruse in electrochromic recording according to claim 1 comprising asupport sheet containing as a color-forming substance a 3-R¹-4-Y-4-[2-R³ -4-(N-R⁴ -N-R⁵ -amino)phenyl]-R-phthalazin-1(2H)-one havingthe structural formula ##STR61## in which R, R¹, R³, R⁴, R⁵ and Y eachhave the same respective meanings given in claim
 1. 3. A substrate foruse in electrochromic recording according to claim 2 comprising asupport sheet containing as a color-forming substance a 3-R¹ -4-[2-R³-4-(N-R⁴ -N-R⁵ -amino)phenyl]-R-phthalazin-1(2H)-one having thestructural formula ##STR62## in which R, R¹, R³, R⁴ and R⁵ each have thesame respective meanings given in claim
 2. 4. A substrate for use inelectrochromic recording according to claim 1 comprising a support sheetcontaining as a color-forming substance a 3-R¹ -[2-R³ -4-(N-R⁴ -N-R⁵-amino)phenyl]-4-[2-R⁹ -4-(N-R¹⁰ -N-R¹¹-amino)phenyl]-R-phthalazin-1(2H)-one having the structural formula##STR63## in which R, R¹, R³, R⁴, R⁵, R⁹, R¹⁰ and R¹¹ each have the samerespective meanings given in claim
 1. 5. A substrate for use inelectrochromic recording according to claim 1 comprising a support sheetcontaining as a color-forming substance a 3-R¹ -4-[2-R³ -4-(N-R⁴ -N-R⁵-amino)phenyl]-4-(1-R¹² -2-R¹³ -5/6-R¹⁴-indol-3-yl)-R-phthalazin-1(2H)-one having the structural formula##STR64## in which R, R¹, R³, R⁴, R⁵, R¹², R¹³ and R¹⁴ each have thesame respective meanings given in claim
 1. 6. A substrate for use inelectrochromic recording according to claim 1 comprising a support sheetcontaining as a color-forming substance a 3-R¹ -4-(1-R⁶ -2-R⁷ -5/6-R⁸-indol-3-yl)-4-(1-R¹² -2-R¹³ -5/6-R¹⁴-indol-3-yl)-R-phthalazin-1(2H)-one having the structural formula##STR65## in which R, R¹, R⁶, R⁷, R⁸, R¹², R¹³ and R¹⁴ each have thesame respective meanings given in claim
 1. 7. A substrate for use inelectrochromic recording comprising a support sheet containing ascolor-forming substances an isomeric mixture of 7-R¹-8-X-8-Y-pyrido-[2,3d]-pyridazin-5(6H)-ones and 5-X-5-Y-6-R¹-pyrido-[2,3d]-pyridazin-8-(5H)-ones having the structural formulas##STR66## wherein: R¹ represents hydrogen, C₁ to C₃ alkyl, pyridyl,##STR67## in which Z is non-tertiary C₁ to C₄ alkoxy, NHNH₂, ornon-tertiary C₁ to C₄ alkyl, phenyl or phenyl substituted by one or twoof C₁ to C₃ alkyl, non-tertiary C₁ to C₄ alkoxy, halo, nitro or amino;Xis selected from the group consisting of ##STR68## Y is selected fromthe group consisting of hydrogen, ##STR69## in which R³ and R⁹independently represent hydrogen, non-tertiary C₁ to C₄ alkyl,non-tertiary C₁ to C₄ alkoxy, acylamido in which acyl is non-tertiary C₂to C₄ alkyl or dialkylamino in which alkyl is non-tertiary C₁ to C₄alkyl, R⁴ and R¹⁰ independently represent non-tertiary C₁ to C₄ alkyl,benzyl or benzyl substituted in the benzene ring by one or two of haloor C₁ to C₃ alkyl, R⁵ and R¹¹ independently represent non-tertiary C₁ toC₄ alkyl, benzyl or benzyl substituted in the benzene ring by one or twoof halo or C₁ to C₃ alkyl, R⁶ and R¹² independently represent hydrogen,non-tertiary C₁ to C₁₆ alkyl, non-tertiary C₂ to C₈ alkylene,phenoxyethyl, benzyl or benzyl substituted in the benzene ring by one ortwo of halo or C₁ to C₃ alkyl, R⁷ and R¹³ independently representhydrogen, C₁ to C₃ alkyl or phenyl, and R⁸ and R¹⁴ independentlyrepresent hydrogen, halo, non-tertiary C₁ to C₄ alkyl, non-tertiary C₁to C₄ alkoxy or nitro.
 8. A substrate for use in electrochromicrecording according to claim 7 comprising a support sheet containing ascolor-forming substances an isomeric mixture of 7-R¹ -8-[2-R³ -4-(N-R⁴-N-R⁵ -amino)phenyl]-8-(1-R¹² -2-R¹³ -5/6-R¹⁴-indol-3-yl)-pyrido-[2,3d]-pyridazin-5(6H)-ones and 5-[2-R³ -4-(N-R⁴-N-R⁵ -amino)phenyl]-5-(1-R¹² -2-R¹³ -5/6-R¹⁴-indol-3-yl)-pyrido-[2,3d]-pyridazin-8(5H)-ones having the structuralformulas ##STR70## in which R¹, R³, R⁴, R⁵, R¹², R¹³ and R¹⁴ each havethe same respective meanings given in claim
 7. 9. A substrate for use inelectrochromic recording according to claim 7 comprising a support sheetcontaining as color-forming substances isomeric mixtures of 7-R¹-8-(1-R⁶ -2-R⁷ -5/6-R⁸ -indol-3-yl)-8-(1-R¹² -2-R¹³ -5/6-R¹⁴-indol-3-yl)-pyrido-[P2,3d]-pyridazin-5(6H)-ones and 5-(1-R⁶ -2-R⁷-5/6-R⁸ -indol-3-yl)-5-(1-R¹² -2-R¹³ -5/6-R¹⁴ -indol-3-yl)-6-R¹-pyrido-[2,3d]-pyridazin-8(5H)-ones having the structural formulas##STR71## in which R¹, R⁶, R⁷, R⁸, R¹², R¹³ and R¹⁴ each have the samerespective meanings given in claim
 7. 10. A substrate for use inelectrochromic recording comprising a support sheet containing as acolor-forming substance a 2-(N-R¹ -amino)-3-X-3-Y-R-phthalimidine havingthe structural formula ##STR72## wherein: R represents hydrogen,dialkylamino in which alkyl is non-tertiary C₁ to C₄ alkyl, COOR² inwhich R² is hydrogen or non-tertiary C₁ to C₁₆ alkyl or one to fourhalo;R¹ represents hydrogen, C₁ to C₃ alkyl, pyridyl, ##STR73## in whichZ is non-tertiary C₁ to C₄ alkoxy, NHNH₂, or non-tertiary C₁ to C₄alkyl, phenyl or phenyl substituted by one or two of C₁ to C₃ alkyl,non-tertiary C₁ to C₄ alkoxy, halo, nitro or amino; X is selected fromthe group consisting of ##STR74## Y is selected from the groupconsisting of hydrogen, ##STR75## in which R³ selects hydrogen,non-tertiary C₁ to C₄ alkyl, non-tertiary C₁ C₄ alkoxy, acylamido inwhich acyl is non-tertiary C₂ to C₄ alkyl or dialkylamino in which alkylis non-tertiary C₁ to C₄ alkyl, R⁴ represents non-tertiary C₁ to C₄alkyl, benzyl or benzyl substituted in the benzene ring by one or two ofhalo or C₁ to C₃ alkyl, R⁵ represents non-tertiary C₁ to C₄ alkyl,benzyl or benzyl substituted in the benzene ring by one or two of haloor C₁ to C₃ alkyl, R⁶ and R¹² independently represent hydrogen,non-tertiary C₁ to C₁₆ alkyl, non-tertiary C₂ to C₈ alkylene,phenoxyethyl, benzyl or benzyl substituted in the benzene ring by one ortwo of halo or C₁ to C₃ alkyl, R⁷ and R¹³ independently representhydrogen, C₁ to C₃ alkyl or phenyl, and R⁸ and R¹⁴ independentlyrepresent hydrogen, halo, non-tertiary C₁ to C₄ alkyl, non-tertiary C₁to C₄ alkoxy or nitro.
 11. A substrate for use in electrochromicrecording according to claim 10 comprising a support sheet containing asa color-forming substance a 2-(N-R¹ -amino)-3-[2-R³ -4-(N-R⁴ -N-R⁵-amino)phenyl]-R-phthalimidine having the structural formula ##STR76##in which R, R¹, R³, R⁴ and R⁵ each have the same respective meaningsgiven in claim
 3. 12. A substrate for use in electrochromic recordingaccording to claim 10 comprising a support sheet containing as acolor-forming substance a 2-(N-R¹ -amino)-3-[2-R³ -4-(N-R⁴ -N-R⁵-amino)phenyl]-3-(1-R¹² -2-R¹³ -5/6-R¹⁴ -indol-3-yl)-R-phthalimidinehaving the structural formula ##STR77## in which R, R¹, R³, R⁴, R⁵, R¹²,R¹³ and R¹⁴ each have the same respective meanings given in claim 10.13. A substrate for use in electrochromic recording according to claim10 comprising a support sheet containing as a color-forming substance a2-(N-R¹ -amino)-3-(1-R⁶ -2-R⁷ -5/6-R⁸ -indol-3-yl)-3-(1-R¹² -2-R¹³-5/6-R¹⁴ -indol-3-yl)-R-phthalimidine having the structural formula##STR78## in which R, R¹, R⁶, R⁷, R⁸, R¹², R¹³ and R¹⁴ each have thesame respective meanings given in claim
 10. 14. A substrate for use inelectrochromic recording comprising a support sheet containing ascolor-forming substances an isomeric mixture of 6-(N-R¹-amino)-7-X-7-Y-(5H)-pyrrolo-[3,4-b]-pyridin-5-ones and 5-X-5-Y-6-(N-R¹-amino)-(7H)-pyrrolo-[3,4-b]-pyridin-7-ones having the structuralformulas ##STR79## wherein: R represents hydrogen, dialkylamino in whichalkyl is non-tertiary C₁ to C₄ alkyl, COOR² in which R² is hydrogen ornon-tertiary C₁ to C₁₆ alkyl or one to four halo;R¹ represents hydrogen,C₁ to C₃ alkyl, pyridyl, ##STR80## in which Z is non-tertiary C₁ to C₄alkoxy, NHNH₂, or non-tertiary C₁ to C₄ alkyl, phenyl or phenylsubstituted by one or two of C₁ to C₃ alkyl, non-tertiary C₁ to C₄alkoxy, halo, nitro or amino; X is selected from the group consisting of##STR81## Y is selected from the group consisting of hydrogen, ##STR82##in which R³ and R⁹ independently represent hydrogen, non-tertiary C₁ toC₄ alkyl, non-tertiary C₁ to C₄ alkoxy, acylamido in which acyl isnon-tertiary C₂ to C₄ alkyl or dialkylamino in which alkyl isnon-tertiary C₁ to C₄ alkyl, R⁴ and R¹⁰ independently representnon-tertiary C₁ to C₄ alkyl, benzyl or benzyl substituted in the benzenering by one or two of halo or C₁ to C₃ alkyl, R⁵ and R¹¹ independentlyrepresent non-tertiary C₁ to C₄ alkyl, benzyl or benzyl substituted inthe benzene ring by one or two of halo or C₁ to C₃ alkyl, R⁶ and R¹²independently represent hydrogen, non-tertiary C₁ to C₁₆ alkyl,non-tertiary C₂ to C₈ alkylene, phenoxyethyl, benzyl or benzylsubstituted in the benzene ring by one or two of halo or C₁ to C₃ alkyl,R⁷ and R¹³ independently represent hydrogen, C₁ to C₃ alkyl or phenyl,and R⁸ and R¹⁴ independently represent hydrogen, halo, non-tertiary C₁to C₄ alkyl, non-tertiary C₁ to C₄ alkoxy or nitro.
 15. A substrate foruse in electrochromic recording according to claim 14 comprising asupport sheet containing as color-forming substances an isomeric mixtureof 6-(N-R¹ -amino)-7-[2-R³ -4-(N-R⁴ -N-R⁵ -amino)phenyl]-7-(1-R¹² -2-R¹³-5/6-R¹⁴ -indol-3-yl)-(5H)-pyrrolo-[3,4-b]-pyridin-5-ones and 5-[2-R³-4-(N-R⁴ -N-R⁵ -amino)phenyl]-5-(1-R¹² -2-R¹³ -5/6-R¹⁴-indol-3-yl)-6-(N-R¹ -amino)-(7H)-pyrrolo-[3,4-b]-pyridin-7-ones havingthe structural formulas ##STR83## in which N, R¹, R³, R⁴, R⁵, R¹², R¹³and R¹⁴ each have the same respective meanings given in claim
 14. 16. Asubstrate for use in electrochromic recording according to claim 14comprising a support sheet containing as color-forming substances anisomer mixture of 6-(N-R¹ -amino)-7-(1-R⁶ -2-R⁷ -5/6-R⁸-indol-3-yl)-7-(1-R¹² -2-R¹³ -5/6-R¹⁴-indol-3-yl)-(5H)-pyrrolo-[3,4-b]-pyridin-5-ones and 5-(1-R⁶ -2-R⁷-5/6-R⁸ -indol-3-yl)-5-(1-R¹² -2-R¹³ -5/6-R¹⁴ -indol-3-yl)-6-(N-R¹-amino)-(7H)-pyrrolo-[3,4-b]-pyridin-7-ones having the structuralformulas ##STR84## in which R¹, R⁶, R⁷, R⁸, R¹², R¹³ and R¹⁴ each havethe same respective meanings given in claim 14.